Antibacterial resin mixture, and preparation method therefor and use thereof

Abstract

The present disclosure relates to the technical field of dental materials, and provides an antibacterial resin mixture, and a preparation method therefor and the use thereof. A resin-infiltrated ceramic composite material prepared by infiltrating the antibacterial resin mixture provided in the present disclosure into a porous ceramic framework and a dental material prepared from a component (2), i.e., the antibacterial resin mixture, can kill oral pathogenic bacteria around a prosthesis and effectively prevent secondary caries; moreover, compared with existing resin-infiltrated ceramic composite materials, the materials have significantly improved mechanical properties, especially significantly improved fracture load, improve the fracture resistance of the existing resin-infiltrated ceramic composite materials, and have good esthetic properties, thereby prolonging the service life of a prosthesis and enabling a prosthesis material to better utilize the properties thereof during service.

Description

An antibacterial resin mixture and its preparation method and application

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] The present disclosure claims the priority of Chinese patent application No. 2024110383653 filed with the Patent Office of China on July 31, 2024, entitled “Antibacterial resin mixture, preparation method and application thereof, resin-infiltrated ceramic composite material and preparation method thereof”; and the priority of Chinese patent application No. 2024103818190 filed with the Patent Office of China on March 29, 2024, entitled “Antibacterial resin mixture, preparation method and application thereof, antibacterial resin, elastic porcelain material and preparation thereof, resin-infiltrated ceramic material and preparation thereof, dental restoration”, the entire contents of which are incorporated by reference into the present disclosure. Technical Field

[0003] The present disclosure relates to the technical field of dental materials, and in particular to an antibacterial resin mixture, a preparation method thereof, and applications thereof. Background Art

[0004] Dental caries is one of the most common chronic diseases in the human oral cavity, primarily caused by daily dietary habits that create an acidic environment in the mouth, gradually corroding tooth tissue. Composite materials, with mechanical properties more similar to those of natural teeth, have become a research hotspot for oral restorations. Resin-infiltrated ceramic composites, in particular, demonstrate superior mechanical properties and aesthetics.

[0005] However, during the process of wearing resin-infiltrated ceramic composite materials in the mouth, they may also be infected by pathogenic bacteria and cause oral diseases due to changes in the oral environment, and the material may break due to eating habits and chewing conditions in the mouth.

[0006] In view of this, the present disclosure is proposed. Summary of the Invention

[0007] The present disclosure aims to provide an antimicrobial resin mixture, its preparation method, and its application. The resin-infiltrated ceramic material prepared using the antimicrobial resin mixture provided herein not only combines aesthetics with excellent antimicrobial properties, but also significantly improves fracture resistance, reducing the occurrence of restoration fracture and secondary caries, and extending the service life of the restoration.

[0008] In order to achieve the above objectives, the present disclosure provides the following technical solutions:

[0009] The embodiment of the present disclosure provides an antibacterial resin mixture, the components of the antibacterial resin mixture are as follows: (1) or (2) component,

[0010] Component (1): 1% to 8% of a first antimicrobial agent, 0.1% to 3% of an initiator, and the balance an acrylate monomer, calculated by weight percentage; based on 100% by weight of the first antimicrobial agent, the first antimicrobial agent is composed of 15% to 25% of an isothiazolinone compound and the balance a polar organic solvent;

[0011] Component (2): Calculated by weight percentage, it consists of 1% to 10% of a second antibacterial agent and 90% to 99% of a resin matrix; based on the weight of the resin matrix being 100%, the resin matrix comprises 0.1% to 3% of an initiator and 97% to 99.9% of an acrylate monomer; based on the weight of the second antibacterial agent being 100%, the second antibacterial agent comprises 15% to 25% of an isothiazolinone compound, 1% to 5% of a coupled modified nano-metal oxide and the remainder being a polar organic solvent.

[0012] The embodiments of the present disclosure further provide a method for preparing the antibacterial resin mixture as described above, comprising the following steps: mixing an acrylate monomer, an initiator, and a first antibacterial agent or a second antibacterial agent to obtain an antibacterial resin mixture.

[0013] The embodiments of the present disclosure further provide a use of the aforementioned antibacterial resin mixture or the antibacterial resin mixture prepared by the aforementioned preparation method in preparing dental materials.

[0014] The embodiments of the present disclosure also provide a resin-infiltrated ceramic composite material, comprising a porous ceramic skeleton and an antibacterial resin infiltrated in the porous ceramic skeleton; the antibacterial resin is formed by curing the aforementioned antibacterial resin mixture or the antibacterial resin mixture prepared by the aforementioned preparation method.

[0015] The embodiments of the present disclosure also provide a method for preparing the resin-infiltrated ceramic composite material as described above, comprising the following steps: impregnating a porous ceramic skeleton into an antibacterial resin mixture for vacuum infiltration, allowing the antibacterial resin mixture to infiltrate the porous ceramic skeleton, and curing to obtain a resin-infiltrated ceramic material; the antibacterial resin mixture is the aforementioned antibacterial resin mixture or the antibacterial resin mixture prepared by the aforementioned preparation method.

[0016] The embodiments of the present disclosure also provide an antibacterial resin obtained by curing an antibacterial resin mixture; the antibacterial resin mixture is the aforementioned antibacterial resin mixture or an antibacterial resin mixture prepared by the aforementioned preparation method; wherein the antibacterial resin mixture is prepared from component (2).

[0017] An embodiment of the present disclosure further provides an elastic porcelain material, comprising a matrix and a filler dispersed in the matrix; the matrix is ​​the aforementioned antibacterial resin; and the filler comprises glass powder.

[0018] The embodiments of the present disclosure further provide a method for preparing the elastic porcelain material as described above, comprising the following steps: mixing an antibacterial resin mixture with a filler to obtain a resin body containing the filler;

[0019] curing the resin containing the filler to obtain an elastic porcelain material;

[0020] The antibacterial resin mixture is the aforementioned antibacterial resin mixture or the antibacterial resin mixture prepared by the aforementioned preparation method.

[0021] An embodiment of the present disclosure also provides a dental restoration made of the aforementioned resin-infiltrated ceramic composite material, the aforementioned antibacterial resin or the aforementioned elastic porcelain material; the dental restoration includes one or more of an inlay, an onlay, a veneer, a single crown and a triple bridge; wherein a conventional porous ceramic skeleton is used in the resin-infiltrated ceramic composite material.

[0022] The beneficial effects of the embodiments of the present disclosure include:

[0023] The antibacterial resin mixture provided by the embodiments of the present disclosure uses isothiazolinone compounds as the active antibacterial ingredient. These compounds can destroy bacterial structures, hinder bacterial nutrient acquisition, effectively kill bacteria, reduce plaque accumulation, and enhance the material's antibacterial ability. They can effectively kill Streptococcus mutans and Porphyromonas gingivalis, the main pathogens that cause dental caries and periodontitis. Furthermore, the first or second antibacterial agent disclosed herein has excellent compatibility with acrylate monomers, and the antibacterial agent has low viscosity and excellent fluidity. This not only enhances the resin's penetration ability but also promotes the polymerization reaction of the resin system, thereby enhancing the material's mechanical properties, including breaking load, strength, hardness, and elastic modulus. Furthermore, the refractive index of the antibacterial agent disclosed herein is not significantly different from that of the ceramic framework, resulting in a colorless composite material and enhanced aesthetic properties of the resin-infiltrated ceramic composite. While ensuring that the resin-infiltrated ceramic composite effectively demonstrates its excellent material properties during service, the present disclosure can also prevent the occurrence of secondary caries, thereby extending the service life of the restoration. DETAILED DESCRIPTION

[0024] The following will be combined with the accompanying drawings in the embodiments of the present disclosure to clearly and completely describe the technical solutions in the embodiments of the present disclosure. Obviously, the embodiments described are only part of the embodiments of the present disclosure, not all of the embodiments. Based on the embodiments of the present disclosure, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present disclosure.

[0025] The embodiment of the present disclosure provides an antibacterial resin mixture, the components of the antibacterial resin mixture are as follows: (1) or (2) component,

[0026] Component (1): 1% to 8% of a first antimicrobial agent, 0.1% to 3% of an initiator, and the balance an acrylate monomer, calculated by weight percentage; based on 100% by weight of the first antimicrobial agent, the first antimicrobial agent is composed of 15% to 25% of an isothiazolinone compound and the balance a polar organic solvent;

[0027] Component (2): Calculated by weight percentage, it consists of 1% to 10% of a second antibacterial agent and 90% to 99% of a resin matrix; based on the weight of the resin matrix being 100%, the resin matrix comprises 0.1% to 3% of an initiator and 97% to 99.9% of an acrylate monomer; based on the weight of the second antibacterial agent being 100%, the second antibacterial agent comprises 15% to 25% of an isothiazolinone compound, 1% to 5% of a coupled modified nano-metal oxide and the remainder being a polar organic solvent.

[0028] In the present disclosure, unless otherwise specified, all raw materials used are commercially available products well known in the art.

[0029] It should be noted that the coupled modified nano-metal oxide and triclosan are omitted from component (1) of the present disclosure. The coupled modified nano-metal oxide will reduce the fracture load, elastic modulus and hardness of the resin-infiltrated ceramic composite material, and will also reduce the linear transmittance of the composite material, affecting the aesthetic performance. Although triclosan can exert a bactericidal effect, it will reduce the degree of resin polymerization and reduce the mechanical properties of the material, especially the fracture load. The present disclosure omits the coupled modified nano-metal oxide and triclosan. The mechanical properties, especially the fracture load, of the prepared resin-infiltrated ceramic composite material are significantly improved while ensuring antibacterial and aesthetic properties, which can reduce the fracture of the restoration and extend the service life of the restoration.

[0030] Optionally, in component (1), the antimicrobial resin mixture provided by the present disclosure includes, by mass percentage, 1% to 8% of the first antimicrobial agent, optionally 2% to 6%, or optionally 3% to 5%. In the embodiments of the present disclosure, specifically 2%, 5%, or 8%. The antimicrobial resin mixture includes 0.1% to 3% of an initiator, optionally 0.5% to 2%, or optionally 1.0% to 1.5%.

[0031] In the present disclosure, the first antimicrobial agent comprises an isothiazolinone compound and a polar organic solvent. The mass content of the isothiazolinone compound in the antimicrobial agent is 15% to 25%, optionally 17% to 23%, with the remainder being the polar organic solvent. In embodiments of the present disclosure, the mass content of the isothiazolinone compound in the antimicrobial agent is specifically 15%, 20%, or 25%.

[0032] Optionally, in component (2), the second antibacterial agent comprises 1% to 10%, optionally 2% to 8%, or optionally 4% to 6%. Based on the mass of the resin matrix as 100%, the resin matrix comprises 97% to 99.9% of the acrylate monomer, optionally 97.5% to 99.5%, or optionally 98% to 99%. Based on the mass of the resin matrix as 100%, the resin matrix comprises 0.1% to 3% of the initiator, optionally 0.5% to 2.5%, or optionally 1% to 2%. The composite antibacterial agent comprises 1% to 5% of the coupled modified nano-metal oxide, optionally 2% to 4%, or optionally 2.5% to 3.5%.

[0033] Optionally, the isothiazolinone compound is one or more of 1,2-benzisothiazolin-3-one (BIT), 2-octyl-4-isothiazolin-3-one (OIT), 2-methyl-4-isothiazolin-3-one (MIT) and 5-chloro-2-methyl-4-isothiazolin-3-one (CMI).

[0034] The present invention innovatively uses isothiazolinone compounds as components of the antibacterial agent. Isothiazolinone compounds have good compatibility with the resin matrix and can enhance the mechanical properties of the resin material, including breaking load, strength, hardness and elastic modulus, especially the breaking load. It can also promote the polymerization reaction of acrylic ester monomers and has a good antibacterial effect.

[0035] Optionally, the acrylic ester monomer includes a main monomer and a diluent monomer.

[0036] In component (1), the mass ratio of the main monomer to the diluent monomer is (1.5-10):1, and can be optionally 1.5-2.5:1. In an embodiment of the present disclosure, the mass ratio of the main monomer to the diluent monomer is 1.5:1 or 2.3:1.

[0037] In component (2), the mass ratio of the main monomer to the diluent monomer is (1.5-4):1, and can be optionally (2-3):1.

[0038] Optionally, the main monomer may include one or more of bisphenol A-glycidyl methacrylate (Bis-GMA), ethoxylated bisphenol A dimethacrylate (Bis-MEPP), N,N-dimethylaniline (DMA) and urethane dimethacrylate (UDMA); the diluent monomer may include one or more of triethylene glycol dimethacrylate (TEGDMA), ethylene glycol dimethacrylate (EGDMA) and trimethylolpropane triacrylate (TMPTMA).

[0039] Optionally, the initiator comprises a thermal initiator and / or a photoinitiator.

[0040] Optionally, the initiator may include a thermal initiator and / or a photoinitiator; the thermal initiator may include one or more of benzoyl peroxide (BPO), tert-butyl peracetate, diisopropyl benzene peroxide (DCP), tert-butyl peroxy-2-ethylhexanoate (TBPO) and tert-butyl perbenzoate (CP-01); the photoinitiator may include one or more of camphorquinone (CQ), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (TPO) and ethyl 2,4,6-trimethylbenzoylphenylphosphonate (TPO-L).

[0041] Optionally, the polar organic solvent is an ester solvent.

[0042] Optionally, the ester solvent includes acetate. Specifically, the ester solvent may be acetate; the acetate may be one or more of methyl acetate, ethyl acetate, butyl acetate, monoacetin, diacetin, and triacetin.

[0043] Optionally, based on 100% by mass of the second antimicrobial agent, the second antimicrobial agent further comprises 0.1% to 0.5%, optionally 0.2% to 0.4%, optionally 0.3% of triclosan. In the present disclosure, triclosan, as an organic antimicrobial component, has good antimicrobial properties.

[0044] It should be noted that the present disclosure has no special requirements for the preparation method of the coupled modified nano-metal oxide, and the coupled modification method well known in the art can be used.

[0045] Optionally, the preparation method of the coupled modified nano metal oxide comprises the following steps: mixing the nano metal oxide with a coupling agent and a solvent, performing coupling modification, and obtaining the coupled modified nano metal oxide.

[0046] Optionally, the coupling agent includes a silane coupling agent; the silane coupling agent may include γ-methacryloxypropyltrimethoxysilane (KH570). In the present disclosure, the solvent may include an ethanol-water mixed solvent; the volume ratio of ethanol to water in the ethanol-water mixed solvent may be (30-50):(1-5). In the present disclosure, the mass of the coupling agent may be 2% to 5% of the mass of the nano-metal oxide. The present disclosure has no special requirements for the amount of solvent used, as long as it can evenly disperse the nano-metal oxide.

[0047] In the present disclosure, the coupling modification can be performed under stirring conditions at room temperature for 2 to 4 hours. After the coupling modification, the present disclosure can filter the resulting product system, wash it with anhydrous ethanol, and dry it to obtain the coupled-modified nanometal oxide. The coupled-modified nanometal oxide can be evenly dispersed in an oily system, preventing agglomeration, which helps improve the mechanical and aesthetic properties of the antibacterial resin.

[0048] Optionally, the nano-metal oxide includes one or more of nano-zinc oxide, nano-silver oxide, nano-yttrium oxide, nano-lanthanum oxide, nano-magnesium oxide, nano-copper oxide, nano-aluminum oxide and nano-iron oxide; the nano-metal oxide used in the present disclosure as the inorganic antibacterial component is more stable than metal elements, and metal elements are more active and easier to agglomerate.

[0049] Optionally, the particle size of the nano metal oxide is 1 nm to 100 nm, optionally 1 nm to 100 nm, or optionally 20 nm to 80 nm.

[0050] It should be noted that the second antibacterial agent in component (2) is a release-type and contact-type antibacterial component of a metal oxide and an organic compound, respectively. The organic antibacterial component can kill bacteria on the surface of the material, reduce plaque accumulation, and enhance the long-term antibacterial ability of the material. In addition, the release of metal ions kills free bacteria outside the material, forming a multi-antibacterial system that can effectively kill Streptococcus mutans and Porphyromonas gingivalis, the main pathogens that cause caries and periodontitis. In addition, the present invention innovatively uses isothiazolinone compounds as components of the antibacterial agent. Isothiazolinone compounds have good compatibility with the resin matrix, can enhance the mechanical properties of the resin material, and have a good antibacterial effect. Furthermore, the composite antibacterial agent disclosed in the present invention has a lower viscosity than the resin matrix and excellent fluidity. Distributing it in the resin matrix can increase the light transmittance of the antibacterial resin and enhance the aesthetic properties of the antibacterial resin.

[0051] The embodiments of the present disclosure further provide a method for preparing the antibacterial resin mixture as described above, characterized in that the method comprises the following steps: mixing an acrylate monomer, an initiator, and a first antibacterial agent or a second antibacterial agent to obtain an antibacterial resin mixture.

[0052] Specifically, when the antibacterial resin mixture is component (1), its preparation method is as follows: first, the acrylic ester monomer and the initiator are stirred in a water bath at 40° C. to 60° C., and then the first antibacterial agent is added and stirred for a second time.

[0053] It should be noted that the present disclosure has no special requirements for the preparation process of the first antimicrobial agent, and the isothiazolinone compound can be directly mixed with the polar organic solvent. Since the isothiazolinone compound itself has a certain viscosity, directly adding it to the resin monomer will cause the viscosity of the resin mixture to increase, which is not conducive to the penetration process, and the performance of the sample formed will decrease; the antimicrobial agent formed by mixing it with the polar organic solvent in the present disclosure has a lower viscosity, which is conducive to the penetration of the resin mixture and thus improves the performance. Optionally, after mixing, the obtained mixture can be vacuum defoamed. The present disclosure has no special requirements for the implementation process of vacuum defoaming, and the vacuum defoaming process well known in the art can be used.

[0054] The present disclosure has no special requirements for the first stirring and the second stirring, as long as the materials are mixed evenly. In the embodiment of the present disclosure, the first stirring rate is 300 r / min and the time is 60 min; the second stirring rate is 300 r / min and the time is 30 min.

[0055] When the antibacterial resin mixture is component (2), its preparation method is as follows: first, the acrylic ester monomer is heated in a water bath at 40° C. to 60° C. and stirred for the first time, then the initiator and the second antibacterial agent are added and stirred for the second time.

[0056] It should be noted that the present disclosure does not require any special preparation process for the second antimicrobial agent; simply thoroughly mix the components of the second antimicrobial agent. The present disclosure prepares the second antimicrobial agent first and then mixes it with the acrylic monomer and initiator to ensure uniform dispersion of the nano-metal oxide. Directly adding the nano-metal oxide to the resin matrix can cause the nano-metal oxide to agglomerate.

[0057] In addition, when preparing the antibacterial resin mixture of component (2) of the present disclosure, the parameters of the first stirring and the second stirring can be the same as those of the antibacterial resin mixture of component (1), and can also be reasonably adjusted according to actual conditions.

[0058] The embodiments of the present disclosure further provide a use of the aforementioned antibacterial resin mixture or the antibacterial resin mixture prepared by the aforementioned preparation method in preparing dental materials.

[0059] Optionally, the dental material comprises an antimicrobial resin, an elastic porcelain material, or a resin-infiltrated ceramic composite.

[0060] It should be noted that the dental material prepared using the antibacterial resin mixture disclosed herein has excellent antibacterial ability and takes into account both mechanical and aesthetic properties; the dental material prepared using component (1) as the raw material has better fracture resistance; optionally, the antibacterial resin and elastic porcelain material in the present disclosure are both prepared based on component (2), and the resin-infiltrated ceramic composite material can be either component (1) or component (2). In other embodiments of the present disclosure, the antibacterial resin and elastic porcelain material can also be prepared based on component (1).

[0061] The embodiments of the present disclosure also provide a resin-infiltrated ceramic composite material, comprising a porous ceramic skeleton and an antibacterial resin infiltrated in the porous ceramic skeleton; the antibacterial resin is formed by curing the aforementioned antibacterial resin mixture or the antibacterial resin mixture prepared by the aforementioned preparation method.

[0062] Optionally, the material of the porous ceramic skeleton includes any one or a combination of at least two of aluminum silicate, feldspar, silicon dioxide, zirconium oxide, tungsten oxide, nepheline and magnesium silicate.

[0063] Optionally, the porous ceramic framework includes a coupling-modified porous ceramic framework or a conventional porous ceramic framework.

[0064] In the present disclosure, when the porous ceramic framework is a coupling-modified porous ceramic framework, it can be a porous ceramic framework modified with a silane coupling agent; the silane coupling agent can optionally include γ-methacryloxypropyltrimethoxysilane (KH570). The purpose of using the coupling-modified porous ceramic framework in the present disclosure is to increase the lipophilicity of the ceramic framework, thereby promoting better bonding of the antibacterial resin to the porous ceramic framework.

[0065] The embodiments of the present disclosure further provide a method for preparing the aforementioned resin-infiltrated ceramic composite material, characterized in that it comprises the following steps: dipping a porous ceramic skeleton into an antibacterial resin mixture and performing vacuum infiltration, allowing the antibacterial resin mixture to infiltrate the porous ceramic skeleton, and curing to obtain a resin-infiltrated ceramic material;

[0066] The antibacterial resin mixture is the aforementioned antibacterial resin mixture or the antibacterial resin mixture prepared by the aforementioned preparation method.

[0067] It should be noted that the present disclosure may optionally provide a porous ceramic skeleton, that is, a conventional porous ceramic skeleton. The present disclosure has no special requirements on the source of the porous ceramic skeleton, and the porous ceramic skeleton may be prepared using methods well known in the art or a commercially available product.

[0068] When a coupled modified porous ceramic skeleton is selected to prepare a resin-infiltrated ceramic composite material, the present disclosure may optionally couple-modify the porous ceramic skeleton before impregnation; the coupling modification may optionally include the following steps: mixing the porous ceramic skeleton with a modifying liquid, followed by vacuuming, pressure-maintaining, and heat-treating in sequence; the modifying liquid includes an alcohol-water mixed solvent, an acid, and a coupling agent.

[0069] In the present disclosure, the alcohol in the alcohol-water mixed solvent may include ethanol, or anhydrous ethanol; the mass ratio of alcohol to water in the alcohol-water mixed solvent may be 1:1. The acid may include any one of acetic acid, oxalic acid, hydrochloric acid, citric acid, and phosphoric acid, or a combination of at least two thereof; the mass of the acid may be 0.5‰ to 3‰, or 1‰ to 2.5‰, of the mass of the alcohol-water mixed solvent; the coupling agent may include a silane coupling agent, the types of which have been discussed above and will not be repeated here; the mass of the coupling agent may be 1% to 10%, or 2% to 6%, of the mass of the alcohol-water mixed solvent.

[0070] In the present disclosure, the mass ratio of the porous ceramic skeleton to the modifying liquid can be selected as 1:3.

[0071] In the present disclosure, the vacuuming time can be selected as 10 minutes to 30 minutes; the pressure holding time can be selected as 20 minutes to 60 minutes. The present disclosure promotes the entry of the modified liquid into the pores of the porous ceramic skeleton by vacuuming and pressure holding.

[0072] In the present disclosure, the heat treatment temperature can be selected from 70° C. to 90° C., or 80° C., and the holding time can be selected from 3 hours to 4 hours. The present disclosure utilizes heat treatment to promote the grafting of the coupling agent to the porous ceramic skeleton.

[0073] After the heat treatment is completed, the present disclosure optionally discards the excess modification liquid and dries the modified porous ceramic skeleton before proceeding to the subsequent steps. In the present disclosure, the drying may be performed by first drying at 50°C for 1 to 3 hours and then drying at 80°C for 2 to 4 hours. The present disclosure utilizes the drying and baking of the modified porous ceramic skeleton.

[0074] In an embodiment of the present disclosure, a conventional porous ceramic skeleton is prepared as follows: 50 g of sodium aluminum silicate powder is poured into a ball mill, 100 g of ethanol and 8 g of a 3% by mass polyvinyl alcohol aqueous solution are added for ball milling, the ball milling speed is 600 r / min, the ball milling time is 2 h, and the obtained ball milled slurry is dried in a 60°C oven for 10 h; the powder is sieved through a 120-mesh stainless steel sieve, the sieved powder is placed in a molding machine, and a ceramic body is obtained by holding the pressure at 3 MPa for 4 min; the ceramic body is pressed for a second time in a cold isostatic press at 220 MPa for 2 min; the ceramic body after the second pressing is placed in a sintering furnace, the temperature is increased to 800°C at a rate of 5°C / min, the temperature is kept for 120 min, and the furnace is cooled to room temperature to obtain a conventional porous ceramic skeleton.

[0075] The preparation method of the coupled modified porous ceramic skeleton is as follows: the conventional porous ceramic skeleton prepared above and the modifying liquid are placed in a beaker at a mass ratio of 1:3, vacuumed in a vacuum box for 20 minutes, then pressure maintained for 20 minutes, placed in an 80°C oven for 3 hours, poured out the modifying liquid, wiped off the excess modifying liquid on the surface of the ceramic skeleton, placed the porous ceramic skeleton in an oven, first dried at 50°C for 1 hour, and then dried at 80°C for 2 hours to obtain a coupled modified porous ceramic skeleton.

[0076] In the present disclosure, the porous ceramic skeleton is immersed in the antibacterial resin mixture and vacuum infiltration is performed to allow the antibacterial resin mixture to completely infiltrate the porous ceramic skeleton and solidify to obtain a resin-infiltrated ceramic composite material.

[0077] The specific vacuum infiltration process can be reasonably selected according to actual needs. Two process solutions are provided in this disclosure, as follows:

[0078] Solution 1: This solution is a step-by-step penetration, as follows:

[0079] The first vacuum infiltration was performed by immersing the antibacterial resin mixture to 1 / 3 of the height of the porous ceramic skeleton, and the second vacuum infiltration was performed by replenishing the antibacterial resin mixture to 2 / 3 of the porous ceramic skeleton, and the third vacuum infiltration was performed by continuing to replenish the antibacterial resin mixture to completely immerse the porous ceramic skeleton. Among them, the pressure of the first vacuum penetration can be selected as 100Pa~1000Pa, can be selected as 100Pa~500Pa, can be selected as 100Pa~200Pa; the time of the first vacuum penetration can be selected as 24h~96h, can be selected as 48h~96h, can be selected as 72h~96h; the pressure of the second vacuum penetration can be selected as 100Pa~1000Pa, can be selected as 100Pa~500Pa, can be selected as 100Pa~200Pa; the time of the second vacuum penetration can be selected as 24h~96h, can be selected as 48h~96h, can be selected as 72h~96h; the pressure of the third vacuum penetration can be selected as 0.1Pa~100Pa, can be selected as 0.1Pa~1Pa; the time of the third vacuum penetration can be selected as 24h~96h, can be selected as 48h~96h, can be selected as 72h~96h.

[0080] It should be noted that step-by-step infiltration is beneficial to promoting the antibacterial resin mixture to better penetrate into the porous ceramic skeleton.

[0081] Solution 2: This solution is a one-step penetration, as follows:

[0082] The pressure of vacuum penetration can be selected from -0.1MPa to 0MPa, and can be selected as -0.1MPa; the time of vacuum penetration can be selected from 48h to 72h, and can be selected as 48h.

[0083] The present disclosure does not specify any specific curing conditions. Curing conditions known in the art can be selected based on the type of initiator in the antibacterial resin mixture. For example, when the initiator is a photoinitiator, the curing conditions may include UV irradiation for 1 to 5 minutes. When the initiator is BPO, which is a thermal initiator, the curing conditions may include: maintaining the temperature at 70°C for 6 hours, then heating the temperature at a rate of 2°C / min to 5°C / min to 100°C and maintaining the temperature for 6 hours.

[0084] Optionally, dipping the coupled modified porous ceramic skeleton into the antibacterial resin mixture for vacuum infiltration includes: submerging the coupled modified porous ceramic skeleton with the antibacterial resin mixture to 1 / 3 of its height for a first vacuum infiltration, replenishing the antibacterial resin mixture to 2 / 3 of the porous ceramic skeleton for a second vacuum infiltration, and continuing to replenish the antibacterial resin mixture to completely submerge the porous ceramic skeleton for a third vacuum infiltration;

[0085] The antibacterial resin mixture is prepared from component (1).

[0086] Optionally, the pressure of the first vacuum penetration is 100Pa~1000Pa, and the time is 24h~96h; the pressure of the second vacuum penetration is 100Pa~1000Pa, and the time is 24h~96h; the pressure of the third vacuum penetration is 0.1Pa~100Pa, and the time is 24h~96h.

[0087] The embodiments of the present disclosure also provide an antibacterial resin obtained by curing an antibacterial resin mixture; the antibacterial resin mixture is the aforementioned antibacterial resin mixture or the antibacterial resin mixture prepared by the aforementioned preparation method; wherein the antibacterial resin mixture is prepared from component (2).

[0088] It should be noted that, before curing, the present disclosure may optionally further include vacuum degassing the antibacterial resin mixture of component (2). The present disclosure has no special requirements for the conditions of vacuum degassing, and vacuum degassing conditions well known in the art may be used.

[0089] The present disclosure does not have any specific requirements for curing conditions; curing conditions known in the art can be selected based on the type of initiator in the antibacterial resin mixture. In the present disclosure, when the initiator is a photoinitiator, the curing conditions may include UV irradiation for 1 to 5 minutes. When the initiator is BPO, which is a thermal initiator, the curing conditions may include: maintaining the temperature at 70°C for 6 hours, then heating the temperature at a rate of 2°C / min to 5°C / min to 100°C and maintaining the temperature for 6 hours.

[0090] The embodiment of the present disclosure also provides an elastic porcelain material, comprising a matrix and a filler dispersed in the matrix; the matrix is ​​an antibacterial resin made from the aforementioned component (2); and the filler comprises glass powder.

[0091] In the present disclosure, the mass content of the filler in the elastic porcelain material can be selected as 60% to 80%, 65% to 75%, or 68% to 72%; the particle size of the filler can be selected as 1 μm to 30 μm, 5 μm to 25 μm, or 10 μm to 20 μm.

[0092] In the present disclosure, the filler includes glass powder; the glass powder may optionally include functional glass powder; the functional glass powder may optionally include one or more of sodium aluminum sulfate powder, boron glass powder, pyrophyllite powder, aluminum silicate fiber powder, silicon micropowder and spodumene powder.

[0093] The present disclosure also provides a method for preparing the elastic porcelain material of the above scheme, comprising the following steps: mixing the antibacterial resin mixture of the above component (2) with a filler to obtain a resin body containing the filler; and curing the resin body containing the filler to obtain the elastic porcelain material.

[0094] The present disclosure has no special requirements for the process of mixing the component (2) antibacterial resin mixture with the filler, as long as the components can be mixed evenly. In the present disclosure, the curing conditions are the same as the curing conditions of the antibacterial resin, and will not be repeated here.

[0095] The embodiments of the present disclosure also provide a dental restoration made of the aforementioned resin-infiltrated ceramic composite material, the antibacterial resin obtained from the aforementioned component (2), or the aforementioned elastic porcelain material; the dental restoration includes one or more of an inlay, an onlay, a veneer, a single crown, and a triple bridge; wherein a conventional porous ceramic skeleton is used in the resin-infiltrated ceramic composite material.

[0096] The present disclosure has no special requirements for the preparation method of the dental restoration, and a preparation method well known in the art can be used, such as cutting by a CAD or CAM system.

[0097] The dental restoration disclosed herein contains an antibacterial resin, exhibits good antibacterial properties, and takes both mechanical and aesthetic properties into consideration.

[0098] The antibacterial resin mixture and its preparation method and application, the resin-infiltrated ceramic composite material and its preparation method provided by the present disclosure are described in detail below in conjunction with the embodiments, but they should not be understood as limiting the scope of protection of the present disclosure.

[0099] Example 1

[0100] This embodiment provides a resin-infiltrated ceramic composite material, which includes a coupled modified porous ceramic skeleton and an antibacterial resin infiltrated into the coupled modified porous ceramic skeleton. The preparation method of the resin-infiltrated ceramic composite material is as follows:

[0101] Preparation of antibacterial resin mixture:

[0102] (1) Weigh Bis-GMA according to Table 1 and place it in a beaker. Then add TEGDMA and BPO to the beaker. Stir the mixture in a 45°C water bath at 300 rpm for 60 min using an electric stirrer to homogenize the solution.

[0103] (2) Add the first antimicrobial agent to the beaker and stir at 300 r / min for 30 min;

[0104] (3) The mixed resin is placed in a vacuum environment to remove bubbles therein to obtain an antibacterial resin mixture.

[0105] Preparation of coupling-modified porous ceramic skeleton:

[0106] (1) Pour 50 g of sodium aluminum silicate powder into a ball mill, add 100 g of ethanol and 8 g of a 3% (mass fraction) polyvinyl alcohol aqueous solution, and mill at a speed of 600 r / min for 2 h. The resulting ball-milled slurry is then dried in an oven at 60°C for 10 h.

[0107] (2) Sieving the powder through a 120-mesh stainless steel sieve, placing the sieved powder in a molding machine, and maintaining the pressure at 3 MPa for 4 minutes to obtain a ceramic green body; the ceramic green body is subjected to a secondary pressing at 220 MPa in a cold isostatic press, and maintaining the pressure for 2 minutes;

[0108] (3) The ceramic green body after secondary pressing was placed in a sintering furnace, heated to 800°C at a rate of 5°C / min, kept at this temperature for 120 min, and cooled to room temperature in the furnace to obtain a porous ceramic skeleton;

[0109] (4) The porous ceramic skeleton and the modifying liquid are placed in a beaker at a mass ratio of 1:3, and the vacuum is drawn in a vacuum box for 20 minutes, and then the pressure is maintained for 20 minutes, and the ceramic skeleton is placed in an oven at 80°C for 3 hours. The modifying liquid is poured out, and the excess modifying liquid on the surface of the ceramic skeleton is wiped dry. The porous ceramic skeleton is placed in an oven, first dried at 50°C for 1 hour, and then dried at 80°C for 2 hours, and the skeleton is dried to obtain a modified porous ceramic skeleton, wherein the composition of the modifying liquid is: the mass ratio of alcohol and water is 1:1, the mass of acetic acid is 1‰ of the mass of the alcohol-water mixed solvent, and the mass of KH570 is 5% of the mass of the alcohol-water mixed solvent.

[0110] Preparation of resin-infiltrated ceramic composites:

[0111] (1) The antibacterial resin mixture is immersed in 1 / 3 of the height of the modified porous ceramic skeleton, and it is placed under low vacuum infiltration at 100Pa for 72 hours. The antibacterial resin mixture is supplemented to immerse it to 2 / 3 of the modified porous ceramic skeleton, and it is placed under low vacuum infiltration at 100Pa for 72 hours. The antibacterial resin mixture is supplemented to completely immerse the modified porous ceramic skeleton, and it is placed under high vacuum infiltration at 1Pa for 72 hours to obtain resin-infiltrated ceramics with good infiltration.

[0112] (2) The infiltrated resin-infiltrated ceramic was placed in an autoclave and kept at 70°C for 6 hours, and then heated to 100°C at a rate of 2°C / min and kept at this temperature for 6 hours for curing to obtain a resin-infiltrated ceramic composite material.

[0113] Examples 2 to 8

[0114] In each example, resin-infiltrated ceramic composite materials were prepared according to the composition ratios of the components shown in Table 1 and Table 2. The preparation method was the same as that in Example 1.

[0115] Table 1 Antibacterial resin mixture formula in Examples 1 to 8

[0116] Table 2 Composition of the first antibacterial agent in Examples 1 to 8

[0117] Example 9

[0118] This embodiment provides an antibacterial resin for dental use. The preparation method of the antibacterial resin is as follows:

[0119] (1) Weigh 29.25 g of Bis-GMA and place it in a beaker. Then add 29.25 g of TEGDMA, 39 g of UDMA, and 0.5 g of BPO to the beaker. Stir the mixture in a 45°C water bath at 300 rpm for 60 min to ensure uniform mixing of the monomers.

[0120] (2) Add 2 g of the second antibacterial agent (composition see Table 3) to the beaker and stir at 300 r / min for 30 min to obtain an antibacterial resin mixture;

[0121] (3) The mixed antibacterial resin mixture is placed in a vacuum environment to remove bubbles therein, and then placed in a heating curve of keeping the mixture at 70°C for 6 hours and heating it to 100°C at a rate of 2°C / min and keeping it for 6 hours to solidify the resin to obtain dental antibacterial resin.

[0122] Examples 10-11

[0123] Dental antibacterial resin was prepared according to the composition ratios shown in Table 3 and Table 4. The preparation method was the same as that in Example 9.

[0124] Example 12

[0125] This embodiment provides an antibacterial elastic porcelain material for dental use. The elastic porcelain material uses the antibacterial resin of Example 9 as a matrix and glass powder as a filler. The preparation method is as follows:

[0126] (1) According to the proportions of the components of the antibacterial resin mixture shown in Tables 3 and 4, the antibacterial resin mixture was prepared using the same method as in Example 9;

[0127] (2) mixing the glass powder and the antibacterial resin mixture with an electric stirrer at 300 r / min for 60 min, wherein the glass powder accounts for 70% of the mass of the elastic porcelain material and the antibacterial resin matrix accounts for 30% of the mass of the elastic porcelain;

[0128] (3) The mixed antibacterial resin matrix containing glass powder is placed in a mold, and then placed in an autoclave and kept at 70°C for 6 hours, and then heated to 100°C at a rate of 2°C / min and kept at this temperature for 6 hours for heating and curing to obtain an elastic porcelain material.

[0129] Example 13

[0130] This embodiment provides a dental antibacterial resin-infiltrated ceramic composite material. The resin-infiltrated ceramic composite material is composed of ceramic material as the main material and resin as the auxiliary material. The preparation method is as follows:

[0131] (1) According to the proportions of the components of the antibacterial resin mixture shown in Tables 3 and 4, the antibacterial resin mixture was prepared using the same method as in Example 9;

[0132] (2) Pour 50 g of sodium aluminum silicate powder (particle size 1 μm to 10 μm) into a ball mill, then add 100 g of ethanol and 8 g of a 3% by mass polyvinyl alcohol aqueous solution and ball mill at a ball mill speed of 600 r / min for 2 h. Then, dry the resulting ball milled slurry in a 60°C oven for 10 h, sieve the powder through a 120-mesh stainless steel sieve, and place the sieved powder in a molding press. Maintain the pressure at 3 MPa for 4 min to obtain a ceramic green body.

[0133] (3) The sodium aluminum silicate ceramic body was subjected to secondary pressing in a cold isostatic press at 220 MPa, and the pressure was maintained for 2 minutes. The ceramic body after secondary pressing was placed in a sintering furnace, heated to 800°C at a rate of 5°C / min, and kept at this temperature for 120 minutes. The conventional porous ceramic body was then cooled to room temperature in the furnace to obtain the conventional porous ceramic body;

[0134] (4) The antibacterial resin mixture was infiltrated in a vacuum environment of -0.1 MPa for 48 hours to allow the antibacterial resin mixture to completely penetrate into the ceramic skeleton, and then heated at 70°C for 6 hours, heated to 100°C at a rate of 2°C / min and kept warm for 6 hours to obtain an antibacterial resin-infiltrated ceramic material.

[0135] Examples 14 to 17

[0136] Dental antibacterial resin was prepared according to the composition ratios shown in Table 3 and Table 4. The preparation method was the same as that in Example 1.

[0137] Table 3 Antibacterial resin mixture formula in Examples 9 to 17

[0138] Table 4 Composition of the second antibacterial agent in Examples 9 to 17

[0139] Comparative Examples 1 to 7

[0140] Each comparative example provides an antibacterial resin-infiltrated ceramic composite material. The antibacterial resin of each comparative example is prepared according to the proportions of the components shown in Table 5 and Table 6, and the preparation method is the same as that of Example 1.

[0141] Table 5 Comparative Examples 1 to 7 Antibacterial Resin Mixture Formula

[0142] Table 6 Composition of the composite antibacterial agent of Comparative Examples 5 to 7

[0143] The composition of the antibacterial agent in Comparative Example 3 is the same as that in Example 3. The modified zinc oxide in Table 6 is coupled modified nano zinc oxide.

[0144] Comparative Example 8

[0145] This comparative example provides an antibacterial resin for dental use. The preparation method of this comparative example is the same as that of Example 9, according to the composition ratios shown in Table 7.

[0146] Comparative Example 9

[0147] This comparative example provides an antibacterial elastic porcelain material for dental use. The elastic porcelain material uses the antibacterial resin of Example 9 as a matrix and glass powder as a filler.

[0148] This comparative example was prepared in the same manner as in Example 12, according to the composition ratios shown in Table 7.

[0149] Comparative Example 10

[0150] This comparative example provides a dental antibacterial resin-infiltrated ceramic material. The resin-infiltrated ceramic material has ceramic material as the main body and resin as the auxiliary material.

[0151] This comparative example was prepared in the same manner as in Example 13 according to the composition ratios shown in Table 7.

[0152] Comparative Examples 11 to 14

[0153] This comparative example provides an antibacterial resin for dental use, which includes a second antibacterial agent, a resin matrix of component (2), and an initiator.

[0154] Each of the comparative examples was prepared in the same manner as in Example 9 according to the composition ratios shown in Table 7.

[0155] Table 7 Comparative Examples 8 to 14 Antibacterial Resin Mixture Ratios

[0156] Among them, the antibacterial agent component in Comparative Example 14 is the same as that in Example 10.

[0157] Performance Testing

[0158] The antibacterial rates of the products prepared in Examples 1-17 and Comparative Examples 1-14 against Streptococcus mutans and Porphyromonas gingivalis were tested in accordance with the standard "JC / T 897-2014 Antibacterial Properties of Antibacterial Ceramic Products." The breaking loads of the resin-infiltrated ceramic composites prepared in Examples 1-8 and Comparative Examples 1-7 were tested using a Shimadzu universal tensile testing machine. The flexural strength and elastic modulus of the products prepared in Examples 1-17 and Comparative Examples 1-14 were tested in accordance with the standard "GB 30367-2013 Dental Ceramic Materials." The hardness of the products prepared in Examples 1-17 and Comparative Examples 1-14 was tested using a Vickers hardness tester. The light transmittance of the products prepared in Examples 1-17 and Comparative Examples 1-14 was tested using a haze meter in accordance with the standard "YY 0271.2-2009 Dental Water-Based Cement" to verify the aesthetic properties of the materials. The test results are summarized in Tables 8-11.

[0159] Table 8 Performance data of resin-infiltrated ceramics of Examples 1-8

[0160] Table 9 Performance data of resin-infiltrated ceramics of Comparative Examples 1-7

[0161] Analysis of the results of Examples 1 to 4 and Comparative Examples 1 to 2 shows that, compared with the case without adding an antibacterial agent, the resin-infiltrated ceramic composite material prepared in the present invention has an antibacterial rate of more than 95% against oral pathogens Streptococcus mutans and Porphyromonas gingivalis. When the amount of antibacterial agent added increases, the antibacterial rate of the antibacterial resin-infiltrated ceramic is more than 99%, both of which have excellent antibacterial properties. The addition of the antibacterial agent significantly enhances the mechanical properties of the resin-infiltrated ceramic, including the breaking load, elastic modulus, hardness and strength, especially the breaking load. However, when the proportion of antibacterial agent added is too high, the mechanical properties of the resin-infiltrated ceramic will be reduced (see Comparative Example 3).

[0162] Analysis of Example 4 and Comparative Example 5 shows that the resin-infiltrated ceramic prepared using OIT combined with triacetin alone exhibits higher mechanical properties, including breaking load, elastic modulus, and hardness, than the resin-infiltrated ceramic prepared using a combination of OIT, modified zinc oxide, and triclosan combined with triacetin. The breaking load is significantly improved, while the linear transmittance is also increased, enhancing the aesthetics. This is primarily because zinc oxide blocks light transmission, while the phenolic structure of triclosan reduces the degree of polymerization of the resin. The combined effect of these two greatly weakens the promoting effect of OIT, ultimately reducing the mechanical and aesthetic properties of the material.

[0163] Analysis of Example 2 and Comparative Example 4 shows that the use of the antibacterial ingredient OIT alone without adding a polar organic solvent will significantly reduce the aesthetic properties and mechanical properties (including breaking load, flexural strength, elastic modulus and hardness) of the resin-infiltrated ceramic composite material; Analysis of Example 2 and Comparative Examples 6-7 shows that the addition of the metal oxide zinc oxide will significantly reduce the hardness, elastic modulus, breaking load and linear transmittance of the material, affecting the aesthetic properties of the material, and the addition of triclosan will significantly reduce the strength, hardness, elastic modulus and breaking load of the material; Analysis of Example 2 and Examples 7-8 shows that OIT is more compatible with the resin system of the present invention than other isothiazolinones such as MIT and CMI, and exhibits better antibacterial and mechanical properties.

[0164] Table 10 Performance data of dental materials prepared in Examples 9 to 17

[0165] Table 11 Performance data of dental materials prepared in Comparative Examples 1 to 7

[0166] Analysis of the results of Examples 9 to 17 and Comparative Examples 8 to 10 shows that the antibacterial rates of the antibacterial resin, antibacterial elastic porcelain, and antibacterial resin-infiltrated ceramic prepared in the present invention against oral pathogens Streptococcus mutans and Porphyromonas gingivalis are all above 95%. When the amount of composite antibacterial agent added increases, the antibacterial rate of the antibacterial resin is above 99%, all of which have excellent antibacterial properties. In addition, the addition of the composite antibacterial agent enhances the mechanical properties and aesthetic properties of the three dental materials.

[0167] From the analysis of the results of Comparative Examples 11 to 13 and Examples 8 to 10, it can be seen that compared with the multi-antibacterial system formed by multiple antibacterial ingredients disclosed in the present invention, the antibacterial rate of a single component is lower, and the addition of a single component will significantly reduce the linear transmittance, strength, and elastic modulus of the resin material, that is, reduce the aesthetic properties and mechanical properties of the material.

[0168] Analysis of the results of Comparative Example 14 and Example 10 shows that when the amount of the second antibacterial agent added is too much, the antibacterial resin will lose some of its own properties, reducing the mechanical properties and aesthetic properties of the material.

[0169] Combined with the data results in Tables 8 to 11, it can also be concluded that the antibacterial resin mixture of the present disclosure omits the coupled modified nano-metal oxide and triclosan. The coupled modified nano-metal oxide will reduce the fracture load, elastic modulus and hardness of the resin-infiltrated ceramic composite material, and will also reduce the linear transmittance of the composite material, affecting the aesthetic performance. Although triclosan can exert a bactericidal effect, it will reduce the degree of resin polymerization and reduce the mechanical properties of the material, especially the fracture load. The resin-infiltrated ceramic composite material prepared by omitting the coupled modified nano-metal oxide and triclosan in the present disclosure has significantly improved mechanical properties, especially the fracture load, while ensuring antibacterial and aesthetic performance, which can reduce the fracture of the restoration and extend the service life of the restoration.

[0170] The above are only optional implementations of the present disclosure. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present disclosure. These improvements and modifications should also be regarded as within the scope of protection of the present disclosure. Industrial Applicability

[0171] The resin-infiltrated ceramic material prepared from the antibacterial resin mixture provided by the present invention has both aesthetics and excellent antibacterial properties, and its fracture resistance is greatly improved, which can reduce the occurrence of restoration fracture and secondary caries and extend the service life of the restoration.

Claims

1. An antibacterial resin mixture, characterized in that: The components of the antibacterial resin mixture are as follows: (1) or (2) component, Component (1): 1% to 8% of a first antibacterial agent, 0.1% to 3% of an initiator, and the balance an acrylate monomer, calculated by weight percentage; based on the weight of the first antibacterial agent being 100%, the first antibacterial agent is composed of 15% to 25% of an isothiazolinone compound and the balance a polar organic solvent; Component (2): Calculated by weight percentage, it consists of 1% to 10% of a second antibacterial agent and 90% to 99% of a resin matrix; based on the weight of the resin matrix as 100%, the resin matrix includes 0.1% to 3% of an initiator and 97% to 99.9% of an acrylate monomer; based on the weight of the second antibacterial agent as 100%, the second antibacterial agent consists of 15% to 25% of an isothiazolinone compound, 1% to 5% of a coupled modified nano-metal oxide and the remainder of a polar organic solvent.

2. The antibacterial resin mixture according to claim 1, characterized in that: The isothiazolinone compound is one or more of 1,2-benzisothiazolin-3-one, 2-octyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one.

3. The antibacterial resin mixture according to claim 1, characterized in that: The acrylic ester monomers include a main monomer and a diluent monomer; In component (1), the mass ratio of the main monomer to the diluent monomer is (1.5-10):1; in component (2), the mass ratio of the main monomer to the diluent monomer is (1.5-4):1; Optionally, the main monomer is one or more of bisphenol A-glycidyl methacrylate, ethoxylated bisphenol A dimethacrylate, N,N-dimethylaniline and urethane dimethacrylate; The diluent monomer is one or more of triethylene glycol dimethacrylate, ethylene glycol dimethacrylate and trimethylolpropane triacrylate.

4. The antibacterial resin mixture according to claim 1, characterized in that: The initiator includes a thermal initiator and / or a photoinitiator; Optionally, the thermal initiator includes one or more of benzoyl peroxide, tert-butyl peroxyacetate, dicumyl peroxide, tert-butyl peroxy-2-ethylhexanoate and tert-butyl perbenzoate; The photoinitiator includes one or more of camphorquinone, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and ethyl 2,4,6-trimethylbenzoylphenylphosphonate.

5. The antibacterial resin mixture according to claim 1, characterized in that: The polar organic solvent is an ester solvent; Optionally, the ester solvent includes acetate.

6. The antibacterial resin mixture according to claim 1, characterized in that: Based on 100% by mass of the second antibacterial agent, the second antibacterial agent further comprises 0.1% to 0.5% of triclosan.

7. The antibacterial resin mixture according to claim 1, characterized in that: The preparation method of the coupled modified nano metal oxide comprises the following steps: mixing the nano metal oxide with a coupling agent and a solvent, performing coupling modification, and obtaining the coupled modified nano metal oxide; Optionally, the coupling agent includes a silane coupling agent; Optionally, the nano metal oxide includes one or more of nano zinc oxide, nano silver oxide, nano yttrium oxide, nano lanthanum oxide, nano magnesium oxide, nano copper oxide, nano aluminum oxide and nano iron oxide; Optionally, the particle size of the nano metal oxide is 1 nm to 100 nm.

8. A method for preparing the antibacterial resin mixture according to any one of claims 1 to 7, characterized in that: The method comprises the following steps: mixing an acrylic acid ester monomer, an initiator and a first antibacterial agent or a second antibacterial agent to obtain the antibacterial resin mixture.

9. Use of the antibacterial resin mixture according to any one of claims 1 to 7 or the antibacterial resin mixture prepared by the preparation method according to claim 8 in the preparation of dental materials.

10. The use according to claim 9, characterized in that The dental material includes antibacterial resin, elastic porcelain material or resin-infiltrated ceramic composite material.

11. A resin-infiltrated ceramic composite material, characterized in that: The invention comprises a porous ceramic skeleton and an antibacterial resin infiltrated in the porous ceramic skeleton; the antibacterial resin is formed by curing the antibacterial resin mixture according to any one of claims 1 to 7 or the antibacterial resin mixture prepared by the preparation method according to claim 8.

12. The resin-infiltrated ceramic composite material according to claim 11, wherein: The material of the porous ceramic skeleton includes any one or a combination of at least two of aluminum silicate, feldspar, silicon dioxide, zirconium oxide, tungsten oxide, nepheline and magnesium silicate.

13. The resin-infiltrated ceramic composite material according to claim 11, characterized in that The porous ceramic skeleton includes a coupled modified porous ceramic skeleton or a conventional porous ceramic skeleton.

14. A method for preparing a resin-infiltrated ceramic composite material according to any one of claims 11 to 13, characterized in that: The following steps are involved: Dipping the porous ceramic skeleton into the antibacterial resin mixture and performing vacuum infiltration, so that the antibacterial resin mixture infiltrates into the porous ceramic skeleton and solidifies to obtain the resin-infiltrated ceramic material; The antibacterial resin mixture is the antibacterial resin mixture according to any one of claims 1 to 7 or the antibacterial resin mixture prepared by the preparation method according to claim 8.

15. The preparation method according to claim 14, characterized in that Impregnating the coupled modified porous ceramic skeleton into the antibacterial resin mixture for vacuum infiltration comprises: submerging the coupled modified porous ceramic skeleton with the antibacterial resin mixture to 1 / 3 of its height for a first vacuum infiltration, replenishing the antibacterial resin mixture to 2 / 3 of the porous ceramic skeleton for a second vacuum infiltration, and continuing to replenish the antibacterial resin mixture to completely submerge the porous ceramic skeleton for a third vacuum infiltration; Wherein, the antibacterial resin mixture is prepared from component (1).

16. The preparation method according to claim 15, characterized in that The pressure of the first vacuum penetration is 100Pa~1000Pa, and the time is 24h~96h; the pressure of the second vacuum penetration is 100Pa~1000Pa, and the time is 24h~96h; the pressure of the third vacuum penetration is 0.1Pa~100Pa, and the time is 24h~96h.

17. An antibacterial resin, characterized in that Obtained by curing an antibacterial resin mixture; the antibacterial resin mixture is the antibacterial resin mixture according to any one of claims 1 to 7 or the antibacterial resin mixture prepared by the preparation method according to claim 8; Wherein, the antibacterial resin mixture is prepared from component (2).

18. An elastic porcelain material, characterized in that: It comprises a matrix and a filler dispersed in the matrix; the matrix is ​​the antibacterial resin according to claim 17; the filler comprises glass powder; Optionally, the mass content of the filler in the elastic porcelain material is 60% to 80%; Optionally, the filler has a particle size of 1 μm to 30 μm.

19. A method for preparing the elastic porcelain material according to claim 18, characterized in that: The following steps are involved: mixing the antibacterial resin mixture with the filler to obtain a resin body containing the filler; curing the filler-containing resin to obtain the elastic porcelain material; The antibacterial resin mixture is the antibacterial resin mixture according to any one of claims 1 to 7 or the antibacterial resin mixture prepared by the preparation method according to claim 8.

20. A dental restoration, characterized in that Made of the resin-infiltrated ceramic composite material according to claim 11, the antibacterial resin according to claim 17, or the elastic porcelain material according to claim 18; the dental restoration comprises one or more of an inlay, an onlay, a veneer, a single crown, and a triple bridge; Wherein, the resin-infiltrated ceramic composite material according to claim 11 uses a conventional porous ceramic skeleton.

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