Non-release antibacterial dental light-cured composite resin as well as preparation method and preparation device thereof

Abstract

The invention relates to non-release antibacterial dental light-cured composite resin and a preparation method thereof. The non-release antibacterial dental light-cured composite resin is formed by compounding a resin matrix, an inorganic filler and a non-release inorganic composite guanidine salt polymer antibacterial agent, wherein the resin matrix comprises a polymerizable monomer system, octavinyl-POSS (Polyhedral Oligomeric Silsesquioxane) and a photoinitiator system; the inorganic filler comprises barium glass powder, fumed silica and needle-like hydroxyapatite, wherein the surface of the barium glass powder is treated by a silane coupling agent KH-570, and the surface of the fumed silica is treated by the silane coupling agent KH-570. The preparation method comprises the following steps: preparing the non-release inorganic composite guanidine salt polymer antibacterial agent, and preparing the non-release antibacterial dental light-cured composite resin. The prepared bacteriostatic dental light-cured composite resin not only meets the requirements of standard YY 1042 in mechanical property, but also has the advantages of safety, broad spectrum, no dissolution, lasting antibacterial effect and the like, and has good market prospect and commercial value.

Description

Technical Field

[0001] This application belongs to the technical field of biomedical polymer materials, and particularly relates to a non-releasing antibacterial dental light-curing composite resin, its preparation method and preparation device. Background Technique

[0002] Dental caries is the most common oral disease among people of all ages. Dental caries is mainly caused by organic acids produced by dental plaque bacteria in the oral cavity. The organic acids create an acidic environment in the teeth, which can gradually lead to the demineralization of tooth enamel. Dental plaque is a bacterial community composed of different bacteria, and there are certain interactions between different bacteria. Among them, Streptococcus mutans (referred to as S. mutans) can promote the conversion of sugars in the diet into extracellular polysaccharides in the oral cavity, providing suitable conditions for the biofilm formation of itself and other bacteria, and it is the main pathogenic microorganism causing dental caries. If dental caries is not treated in time, the lesion will develop into a cavity, which may cause pulpitis, periapical periodontitis, alveolar bone and jaw bone inflammation, and even lead to tooth loss, affecting the oral health and daily life of patients. Filling and repairing the carious site is the main treatment method for dental caries clinically. Currently, the dental filling and repairing materials used clinically are mainly resin-based filling and repairing materials. Resin-based dental composites have become the main filling or bonding materials for the treatment of tooth defects due to their excellent aesthetics, good mechanical properties, bonding strength and ease of operation. However, the polymerization shrinkage of composite resin materials is likely to cause microleakage and accumulate bacterial plaque, resulting in secondary caries in tooth tissues. Endowing the filling, repairing and bonding materials with antibacterial properties is one of the important ways to solve this problem. In recent years, the antibacterial composite resins studied have had an adverse effect on the long-term antibacterial effect due to the release of antibacterial agents. Therefore, finding effective methods to maintain the long-term antibacterial effect of composite resins is an urgent problem to be solved in the field of oral materials. The synthetic antibacterial agents added to composite resins mainly include metals and their oxides, quaternary ammonium salts, and antibiotics. According to the action mode of their antibacterial properties, these antibacterial agents can be divided into non-release type, release type, and release and non-release mixed type. Non-release type antibacterial agents, such as methacryloyloxydecylpyridinium bromide (MDPB), quaternary ammonium dimethacrylate (QADM), dimethyldodecylammonium methacrylate (DMADDM), etc. Non-release type antibacterial agents copolymerize with resin monomers and will not cause a decrease in antibacterial efficiency with time release, and adding an appropriate dose will not affect the mechanical properties and cytotoxicity. However, non-release type antibacterial agents have a weak inhibitory effect on bacteria far from the resin surface. Releaseable antibacterial agents, such as silver nanoparticles (AgNPs), ZnO nanoparticles. Release type antibacterial agents not only inhibit the growth of bacteria on the resin surface, but also inhibit the bacteria suspended in the culture medium far from the resin surface. However, with the complete release of the antibacterial agent, the antibacterial properties of the release type antibacterial agent will disappear, and dental resins require a long-term stable antibacterial effect. The rapid release affects the long-term antibacterial effect of these materials, and a too large short-term release amount will increase the cytotoxicity of the materials.Another problem with the release-type antibacterial agent is that the nanoparticles in dental resins tend to aggregate, which affects the stable release of the nanoparticles and may have a negative impact on the mechanical properties of the resins. In addition, the biosafety of silver nanoparticles is also worthy of attention. Excessive silver may accumulate in tissues such as the skin, liver, and kidneys, which can affect human health. Moreover, as the concentration of nano silver in the resin increases, the color exhibited by the material will become darker and darker, which is not conducive to oral aesthetics.

[0003] In recent years, the organic polymer antibacterial agents that have been studied more include guanidine salt polymers, quaternary ammonium salt polymers, quaternary phosphonium salt polymers, organotin polymers, etc. Among them, compared with other types of organic polymer antibacterial agents, the antibacterial agents containing guanidine salt polymers have lower toxicity, better high-temperature resistance, and excellent antibacterial and antifungal properties. Therefore, they are considered to have great development potential. Guanidine salt polymers are cationic polyelectrolytes with guanidine salt groups. They mainly form electrostatic adsorption through the cations in the molecule and the anionic sites on the surface of bacterial cells, hinder the action of harmful microbial cell lysing enzymes, and deform the surface structure of the cells to damage the cell membrane, thereby achieving the effect of inhibiting and killing microorganisms. Guanidine salt polymers have the advantages of good water solubility, photothermal stability, high-efficiency and broad-spectrum antibacterial properties, safety, low toxicity, non-irritating, non-producing bacterial drug resistance, non-volatile, free of heavy metals and phenols, non-corrosive to various treated surfaces, and environmentally friendly. They have been widely used in medical disinfection, sterilization and disinfection of food and other daily necessities. Since the guanidine group is a hydrophilic group, most guanidine salt polymers have strong water solubility. At present, they are mainly used in the surface disinfection treatment of products and the post-antibacterial finishing of textiles in the form of aqueous solutions of guanidine salt polymers. However, when guanidine salt polymers are directly used as antibacterial agents for resin-based dental composites, the products will gradually lose their antibacterial properties due to poor water resistance because they are soluble in water. Therefore, how to improve the anti-precipitation and persistence of the antibacterial dental composites containing guanidine salt polymers while maintaining the advantages of guanidine salt polymers against harmful microorganisms is a very worthy research topic.

[0004] Therefore, it is necessary to develop an antibacterial and bacteriostatic photocurable dental composite resin based on a non-release-type guanidine salt polymer antibacterial agent with high antibacterial efficiency, anti-precipitation, and long-lasting antibacterial performance, which has high economic and social value. Summary of the Invention

[0005] To solve the above problems, the present application provides a non-release-type antibacterial and bacteriostatic dental photocurable composite resin, its preparation method and preparation device. The non-release-type antibacterial and bacteriostatic photocurable composite resin uses a new type of non-release-type inorganic composite guanidine salt polymer as an antibacterial agent, and the addition amount is about 1% - 2%. The prepared non-release-type antibacterial and bacteriostatic photocurable composite resin not only meets the requirements of standard YY 1042 in terms of mechanical properties, but also has the advantages of safety, broad-spectrum, non-dissolution, and long-lasting antibacterial effect.

[0006] The technical solution adopted in this application is as follows:

[0007] This non-release antibacterial dental light-curing composite resin of this application is composed of the following components in parts by weight:

[0008] Resin matrix: 15 - 35 parts

[0009] Inorganic filler: 65 - 85 parts

[0010] Non-release inorganic composite guanidine salt polymer antibacterial agent: 0.5 - 1.5 parts;

[0011] The resin matrix is composed of a photoinitiator system with a mass percentage of 1% - 2%, octavinyl-POSS with a mass percentage of 1% - 2%, and the balance of a polymerizable monomer system;

[0012] Among them, the photoinitiator system is composed of a main initiator and an initiation promoter with a mass ratio of 1:1 - 4. The main initiator is camphorquinone, and the initiation promoter is N,N-diethylaminoethyl benzoate EDMAB or N,N-dimethylaminoethyl methacrylate DMAEMA;

[0013] The polymerizable monomer system is composed of a polyfunctional methacrylate monomer and a diluent monomer with a mass ratio of 1 - 2:1. The polyfunctional methacrylate monomer is selected from at least one of bisphenol A diglycidyl methacrylate Bis-GMA and bisphenol A ethyl methacrylate Bis-EMA, and the diluent monomer is triethylene glycol dimethacrylate TEGDMA, bis-trimethylolpropane tetraacrylate TMPTMA, ethylene glycol dimethacrylate EDMA, or 2-hydroxyethyl methacrylate HEMA;

[0014] The inorganic filler is composed of barium glass powder treated with 80% by mass of surface silane coupling agent KH-570, fumed silica treated with 17% by mass of surface silane coupling agent KH-570, and acicular hydroxyapatite with a mass percentage of 3%. Among them, the average particle size of the barium glass powder is 0.7 μm, the average particle size of the fumed silica is 40 nm, and the average particle size of the acicular hydroxyapatite is 20 nm - 60 nm;

[0015] The non-release inorganic composite guanidine salt polymer antibacterial agent is prepared by compounding epoxy group-functionalized silica, guanidine salt polymer, polyether polyol, methyl silicone oil, and zinc ricinoleate.

[0016] Further, the epoxy group-functionalized silica is a functionalized silica obtained by grafting epoxy groups onto the surface of silica powder through a chemical reaction using an epoxy group-containing silane coupling agent, and the organic part of the epoxy group-functionalized silica accounts for 10% to 30% of the total mass of the epoxy group-functionalized silica after being calcined at a high temperature above 600°C; wherein, the epoxy group-containing silane coupling agent is selected from one or more of γ-glycidoxypropyltrimethoxysilane, 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)-ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, or 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane;

[0017] The polyether polyol is selected from one or more of polypropylene oxide polyol, polyethylene oxide polyol, polytriethylene glycol, or polytetrahydrofuran and its copolymerized ether diol;

[0018] The guanidine salt polymer is selected from one or more of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, polyhexamethylene guanidine propionate, polyhexamethylene biguanide propionate, polyhexamethylene guanidine nitrate, polyhexamethylene biguanide nitrate, polyhexamethylene guanidine phosphate, polyhexamethylene biguanide phosphate, polyhexamethylene guanidine carbonate, or polyhexamethylene biguanide carbonate;

[0019] In the non-releasing inorganic composite guanidine salt polymer antibacterial agent, the mass content of the polyether polyol is 3% to 35%, the mass content of the methyl silicone oil is 0.5% to 10%, the mass content of zinc ricinoleate is 1% to 10%, and the mass ratio of the epoxy group-functionalized silica to the guanidine salt polymer is 1:2 to 10:1.

[0020] Based on the same inventive concept, the present application also provides a method for preparing the above non-releasing antibacterial dental light-curing composite resin, including the following preparation steps:

[0021] S1. Operate under the protection of a pale yellow safety light source. First, mix the multifunctional methacrylate monomer and the diluent monomer evenly, and then add the main initiator and the initiator accelerator, and stir well to obtain a viscous resin solution;

[0022] S2. Mix evenly the barium glass powder treated with the surface silane coupling agent KH-570, the fumed silica treated with the surface silane coupling agent KH-570, the acicular hydroxyapatite, the non-releasing inorganic composite guanidine salt polymer antibacterial agent, and the octavinyl-POSS powder;

[0023] S3. Operate under the protection of a pale yellow safety light source. Add the solid powder mixed in S2 to the viscous resin glue solution in portions. First, premix it using a double-center mixing and dispersing machine, then put the premixed composite resin into a three-roll grinding machine with a spatula for further uniform mixing, and collect it with a trowel. Finally, fully stir it evenly in a vacuum mixer to eliminate air bubbles, and the uncured composite resin paste is obtained.

[0024] S4. Finally, after curing with visible blue light with a wavelength of 400 - 500 nm for 30 - 180 s, a non-release antibacterial dental light-curing composite resin is obtained.

[0025] Furthermore, the preparation method of the non-release inorganic composite guanidine salt polymer antibacterial agent in step S2 includes the following steps:

[0026] S10. Add epoxy group-functionalized silica, guanidine salt polymer, polyether polyol, and methyl silicone oil to a kneader equipped with an ultrasonic generator. Protect it by introducing an inert gas at normal pressure. Start stirring at room temperature to mix the materials evenly. Then raise the temperature and stir to melt the polymer materials and mix them evenly with the epoxy group-functionalized silica. At the same time, start the ultrasonic generator of the kneader. Under the action of ultrasonic waves, promote the full dispersion of the epoxy group-functionalized silica in the molten materials for reaction, and maintain the reaction temperature of 100 - 200 °C for 1 - 8 hours. Then, keep the original reaction temperature of the kneader, the agitator, and the ultrasonic generator working, turn off the inert gas, perform vacuum degassing for 1 - 3 hours, then introduce the inert gas to normal pressure, add zinc ricinoleate, and continue stirring for 0.5 - 2 hours under the protection of the inert gas.

[0027] S11. After the reaction in step S10 ends, cool the molten product to room temperature, and then crush the cooled solid product into powder.

[0028] S12. Then disperse the product crushed in step S11 in distilled water to form a suspension, filter and separate the solid product, wash it with an organic solvent, and then dry and crush the separated solid product into powder to prepare the non-release inorganic composite guanidine salt polymer antibacterial agent.

[0029] Among them, the organic solvent in step S12 is selected from methanol, ethanol, or acetone, and the inert gas in step S10 is nitrogen or argon.

[0030] The non-release inorganic composite guanidine salt polymer antibacterial agent provided by this application binds the high molecular chain of the guanidine salt polymer to the surface of inorganic silica powder particles through chemical bonding. Utilizing the property that the silica powder particles are insoluble in water, the prepared non-release inorganic composite guanidine salt polymer antibacterial agent also has the property of being insoluble in water, solving the problem of poor water solubility resistance of the guanidine salt polymer added to the polymer material. Moreover, due to the property of being insoluble in water, the inorganic composite guanidine salt polymer antibacterial agent prepared in this application has non-release property. After being added to the photocurable dental composite resin, it has advantages such as anti-dissolution property and long-lasting antibacterial effect.

[0031] Based on the same inventive concept, this application also provides a preparation device for the above preparation method, including an ultrasonic kneading component;

[0032] The ultrasonic kneading component is provided with a cylinder body, multiple groups of ultrasonic generators, inert pipe fittings, and vacuum pipe fittings. The cylinder body is provided with a feeding port, and the feeding port is provided with a sealing cover. Multiple groups of the ultrasonic generators are arranged on the side of the cylinder body. The inert pipe fittings are installed on the cylinder body for introducing or discharging inert gas. The vacuum pipe fittings are installed on the cylinder body for extracting the air inside the cylinder body. Control valves are respectively installed on the inert pipe fittings and the vacuum pipe fittings;

[0033] Furthermore, the frequencies of multiple groups of the ultrasonic generators are respectively set to 20 kHz, and the power adjustment range of a single ultrasonic generator in multiple groups of the ultrasonic generators is 0 - 500 W.

[0034] The beneficial effects of this application are as follows:

[0035] 1. The non-release antibacterial dental photocurable composite resin provided by this application not only meets the requirements of standard YY1042 in terms of mechanical properties, but also has advantages such as safety, broad spectrum, non-dissolution, and long-lasting antibacterial effect, and has good market prospects and commercial value.

[0036] 2. The preparation method of the non-release antibacterial dental photocurable composite resin provided by this application has a simple technological process and is easy to prepare, meeting the requirements of mass production and manufacturing.

[0037] 3. The preparation device provided by this application has a simple structure, reasonable design, is convenient for vacuum adjustment and introduction of inert gas protection during the preparation process, and has good application effects. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 It is a schematic structural diagram of the ultrasonic kneading component in this application;

[0039] Description of reference numerals: ultrasonic kneading member 100, cylinder block 110, ultrasonic generator 120, inert pipe fitting 130, vacuum pipe fitting 140. Detailed implementation mode

[0040] The present application will be further described below in conjunction with preferred embodiments.

[0041] Embodiment 1:

[0042] The non-release antibacterial dental photocurable composite resin provided in this embodiment is prepared by the following steps:

[0043] S1. Prepare the non-release inorganic composite guanidine salt polymer antibacterial agent powder 1# for standby;

[0044] S10. Add 1000 g of fumed silica that has been pre-dried at 120°C for 5 hours to an aqueous solution of 30 L of absolute ethanol (the mass ratio of absolute ethanol to distilled water is 3:1), adjust the pH value to 4-5 with hydrochloric acid, start stirring and assist with an ultrasonic environment to make it evenly dispersed for 30 min, then slowly drop 200 g of γ-glycidoxypropyltrimethoxysilane (CAS No.: 2530-83-8), and then raise the temperature to 70°C. After stirring at a constant temperature for 10 hours, filter the fumed silica suspension, wash it 3 times with absolute ethanol, dry and grind it to obtain epoxy group-functionalized fumed silica for storage and standby. Take a sample and place it for a high-temperature test at 600°C for 5 hours, and the weight loss rate is 10.2%;

[0045] Put 600 g of the above-prepared epoxy group-functionalized fumed silica, 750 g of polyhexamethylene guanidine hydrochloride (average molecular weight 10000), 90 g of polypropylene triol (hydroxyl value 53-59), and 45 g of methyl silicone oil into the cylinder block of a kneader equipped with an ultrasonic generator. Cover the cylinder head, replace the vacuum with nitrogen several times, then open the stainless steel gas valve, and introduce nitrogen at normal pressure for protection. Start stirring at room temperature to make the materials mix evenly, raise the temperature and stir to melt the polymer materials and mix them evenly with the epoxy group-functionalized fumed silica. At the same time, start the ultrasonic generator on the side of the kneader cylinder block. Under the action of ultrasonic waves, promote the epoxy group-functionalized fumed silica to be fully dispersed in the molten materials for reaction, and maintain the reaction temperature of 180°C for 3 hours. Then, keep the original reaction temperature of the kneader, the action of the stirrer and the ultrasonic generator, close the inert gas inlet and outlet valve on the kneader cylinder head, open the vacuum tube valve on the cylinder head and start the vacuum. After vacuum degassing for 1.5 hours, relieve the vacuum in the cylinder, introduce nitrogen to normal pressure, open the solid feeding port on the cylinder head, add 15 g of zinc ricinoleate, and continue stirring for 1.5 hours under nitrogen protection;

[0046] S11. After the reaction in step S10 is completed, cool the molten product to room temperature, and then crush the cooled solid product into powder.

[0047] S12. Then disperse the product crushed in step S11 in distilled water to form a suspension, filter and separate the solid product, wash it with acetone solvent, and then dry and crush the separated solid product into powder to prepare a non-releasing inorganic composite guanidine salt polymer antibacterial agent, and prepare the powder 1# of the non-releasing inorganic composite guanidine salt polymer antibacterial agent of Example 1;

[0048] S2. Preparation of non-releasing antibacterial dental light-curing composite resin:

[0049] According to the formula shown in Table 1, operate under the protection of a pale yellow safety light source. First, mix Bis-GMA and TEGDMA evenly, then add CQ and EDMAB, and stir well to obtain a viscous resin glue;

[0050] Then mix evenly the barium glass powder treated with the surface silane coupling agent KH-570, the fumed silica treated with the surface silane coupling agent KH-570, the needle-like hydroxyapatite, the powder 1# of the non-releasing inorganic composite guanidine salt polymer antibacterial agent, and the octavinyl-POSS powder;

[0051] Then, operate under the protection of a pale yellow safety light source, add the above-mentioned mixed solid powder to the viscous resin glue in batches, first premix with a double-center mixing and dispersing machine, then put the premixed composite resin into a three-roll mill with a spatula for further mixing evenly, collect it with a spatula, and finally stir well in a vacuum mixer to eliminate air bubbles, and obtain an uncured composite resin paste.

[0052] Finally, after visible blue light curing at a wavelength of 430 - 490 nm for 90 s, a non-releasing antibacterial dental light-curing composite resin is obtained.

[0053] Table 1 Components and contents of the non-releasing antibacterial dental light-curing composite resin in Example 1

[0054]

[0055] Characterization of the non-releasing antibacterial dental light-curing composite resin in this example: Refer to the pharmaceutical industry standard "YY1042 - 2011", the flexural strength of this dental composite resin is tested to be 105 MPa. Refer to the national standard "GB / T31402 - 2015", the antibacterial rate of this dental composite resin against Streptococcus mutans, the main cariogenic bacterium in the oral cavity, is 92.5%. Refer to the national standard "GB21551.1 - 2008", the width of the antibacterial zone of this dental composite material is tested to be 0 mm.

[0056] Example 2:

[0057] In this example, the prepared product is a non - release antibacterial dental light - cured composite resin.

[0058] The non - release inorganic composite guanidine salt polymer antibacterial agent powder 1# was prepared through the same preparation process as in Example 1.

[0059] According to the formula shown in Table 2, under the protection of a pale - yellow safety light source, the same preparation method as in Example 1 was adopted.

[0060] Table 2 Components and their contents of the non - release antibacterial dental light - cured composite resin in Example 2

[0061]

[0062] Characterization of the non - release antibacterial dental light - cured composite resin in this example: Referring to the pharmaceutical industry standard "YY1042 - 2011", the flexural strength of this dental composite resin was tested to be 101 MPa. Referring to the national standard "GB / T31402 - 2015", the antibacterial rate of this dental composite resin against Streptococcus mutans, the main cariogenic bacterium in the oral cavity, was tested to be 99.9%. Referring to the national standard "GB21551.1 - 2008", the width of the antibacterial zone of this dental composite material was tested to be 0 mm.

[0063] Example 3:

[0064] The non - release antibacterial dental light - cured composite resin provided in this example is prepared through the following steps:

[0065] S1. Prepare the non - release inorganic composite guanidine salt polymer antibacterial agent powder 2# for later use:

[0066] Except that 750 g of polyhexamethylene guanidine propionate (average molecular weight 10000) was used to replace 750 g of polyhexamethylene guanidine hydrochloride, the others were the same as the non - release inorganic composite guanidine salt polymer antibacterial agent powder 1# in Example 1.

[0067] S2. Preparation of the non - release antibacterial dental light - cured composite resin:

[0068] According to the formula shown in Table 3, under the protection of a pale - yellow safety light source, the same preparation method as in Example 1 was adopted.

[0069] Table 3 Components and their contents of the non - release antibacterial dental light - cured composite resin in Example 3

[0070]

[0071] Characterization of the non-release antibacterial dental light-curing composite resin of this embodiment: Referring to the pharmaceutical industry standard "YY 1042-2011", the flexural strength of this dental composite resin was tested to be 102 MPa. Referring to the national standard "GB / T 31402-2015", the antibacterial rate of this dental composite resin against Streptococcus mutans, the main cariogenic bacterium in the oral cavity, was tested to be 99.9%. Referring to the national standard "GB 21551.1-2008", the width of the antibacterial zone of this dental composite material was tested to be 0 mm.

[0072] From the test data of the above Examples 1-3, it can be seen that the flexural strength of all samples meets the requirements of the pharmaceutical industry standard "YY 1042-2011" (not less than 80 MPa), and the width of the antibacterial zone of all samples is 0 mm, which indicates that the inorganic composite guanidine salt polymer antibacterial agent of this application has excellent non-dissolution properties and meets the requirements of non-release antibacterial agents. Moreover, the antibacterial rate of all samples against Streptococcus mutans is >90%, meeting the requirements of antibacterial materials. And when the addition amount of the non-release inorganic composite guanidine salt polymer antibacterial agent powder is 1%, the antibacterial rate reaches 99.9%, showing excellent antibacterial effects. The antibacterial dental light-curing composite resin prepared by the present invention not only meets the requirements of standard YY 1042 in terms of mechanical properties, but also has the advantages of safety, broad spectrum, non-dissolution, and long-lasting antibacterial effects, and has good market prospects and commercial value.

[0073] See the appendix Figure 1 As shown, the preparation device provided by this application includes an ultrasonic kneading component 100;

[0074] The ultrasonic kneading component 100 is provided with a cylinder body 110, multiple groups of ultrasonic generators 120, inert pipe fittings 130, and vacuum pipe fittings 140. The cylinder body 110 is provided with a feeding port, and the feeding port is provided with a sealing cover body. Multiple groups of ultrasonic generators are arranged on the side of the cylinder body 110. The inert pipe fittings 130 are installed on the cylinder body 110 for introducing or discharging inert gas, and the vacuum pipe fittings 140 are installed on the cylinder body 110 for pumping out the air in the cylinder body 110. Control valves are respectively installed on the inert pipe fittings 130 and the vacuum pipe fittings 140;

[0075] Specifically, the frequencies of multiple groups of ultrasonic generators 120 are respectively set to 20 kHz, and the power adjustment range of a single ultrasonic generator in multiple groups of ultrasonic generators 120 is 0-500 W.

[0076] The preparation device provided by this application has a simple structure, reasonable design, is convenient for vacuum adjustment and introduction of inert gas protection during the preparation process, and has good application effects.

[0077] The above-described embodiments merely represent several implementation manners of the present application. The description thereof is relatively specific and detailed, but it should not be construed as a limitation on the patent scope of the present application. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present application, several modifications and improvements can still be made, and these all fall within the protection scope of the present application. Therefore, the protection scope of the patent of the present application shall be subject to the appended claims.

Claims

1. A non-release antibacterial dental light-curing composite resin, characterized in that: It is composed of the following components in parts by weight: Resin matrix 15-35 parts Inorganic filler 65-85 parts 0.5-1.5 parts of non-releasing inorganic composite guanidine salt polymer antibacterial agent; The resin matrix is ​​composed of a photoinitiator system with a mass percentage of 1% to 2%, octavinyl-POSS with a mass percentage of 1% to 2%, and a polymerizable monomer system as the balance; The photoinitiator system is composed of a main initiator and an initiator accelerator in a mass ratio of 1:1 to 4, the main initiator is camphorquinone, and the initiator accelerator is N,N-dimethylaminobenzoic acid ethyl ester EDMAB or N,N-dimethylamino ethyl methacrylate DMAEMA; The polymerizable monomer system is composed of a multifunctional methacrylate monomer and a diluent monomer in a mass ratio of 1 to 2:1, wherein the multifunctional methacrylate monomer is selected from at least one of bisphenol A dimethacrylate glycidyl Bis-GMA and bisphenol A ethyl methacrylate Bis-EMA, and the diluent monomer is triethylene glycol dimethacrylate TEGDMA, ditrimethylolpropane acrylate TMPTMA, ethylene glycol dimethacrylate EDMA or hydroxyethyl methacrylate HEMA; The inorganic filler is composed of 80% by weight of barium glass powder treated with surface silane coupling agent KH-570, 17% by weight of fumed silica treated with surface silane coupling agent KH-570, and 3% by weight of needle-shaped hydroxyapatite, wherein the average particle size of the barium glass powder is 0.7 μm, the average particle size of the fumed silica is 40 nm, and the average particle size of the needle-shaped hydroxyapatite is 20 nm to 60 nm; The non-releasing inorganic composite guanidine salt polymer antibacterial agent is prepared by compounding epoxy group-functionalized white carbon black, guanidine salt polymer, polyether polyol, methyl silicone oil and ricinoleate zinc.

2. The non-release antibacterial dental light-curing composite resin according to claim 1, characterized in that: The epoxy group functionalized silica is a silica functionalized by grafting epoxy groups on the surface of silica powder through a chemical reaction using an epoxy silane coupling agent, and the epoxy group functionalized silica can be burned at a high temperature above 600°C, and the organic part accounts for 10% to 30% of the total mass of the epoxy group functionalized silica; wherein the epoxy silane coupling agent is selected from one or more of γ-glycidyloxypropyltrimethoxysilane, 3-(2,3-epoxypropyloxy)propylmethyldimethoxysilane, γ-glycidyloxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)-ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane or 3-(2,3-epoxypropyloxy)propylmethyldiethoxysilane; The polyether polyol is selected from one or more of polyoxypropylene polyol, polyoxyethylene polyol, polytrimethyl ether glycol or polytetrahydrofuran and copolyether glycol thereof; The guanidine polymer is selected from one or more of polyhexamethyleneguanidine hydrochloride, polyhexamethylenebiguanidine hydrochloride, polyhexamethyleneguanidine propionate, polyhexamethylenebiguanidine propionate, polyhexamethyleneguanidine nitrate, polyhexamethylenebiguanidine nitrate, polyhexamethyleneguanidine phosphate, polyhexamethylenebiguanidine phosphate, polyhexamethyleneguanidine carbonate or polyhexamethylenebiguanidine carbonate; In the non-releasing inorganic composite guanidine polymer antibacterial agent, the mass content of the polyether polyol is 3% to 35%, the mass content of the methyl silicone oil is 0.5% to 10%, the mass content of the zinc ricinoleate is 1% to 10%, and the mass ratio of the epoxy group functionalized white carbon black to the guanidine polymer is 1:2 to 10:

1.

3. The method for preparing the non-release antibacterial dental light-curing composite resin according to any one of claims 1 to 2, characterized in that: The method comprises the following preparation steps: S1. Under the protection of a light yellow safety light source, the multifunctional methacrylate monomer and the diluent monomer are first mixed evenly, and then the primary initiator and the initiator accelerator are added, and stirred thoroughly to obtain a viscous resin glue; S2. The barium glass powder treated with a surface silane coupling agent KH-570, the fumed silica treated with a surface silane coupling agent KH-570, the needle-shaped hydroxyapatite, the non-releasing inorganic composite guanidine polymer antibacterial agent and the octavinyl-POSS powder are mixed uniformly; S3. Operate under the protection of a light yellow safety light source, add the solid powder mixed in S2 to the viscous resin glue in batches, first use a dual-center mixing and dispersing machine for premixing, then use a scraper to put the premixed composite resin into a three-roll grinder for further mixing, and collect it with a spatula, and finally stir it thoroughly in a vacuum mixer to eliminate bubbles, so as to obtain an uncured composite resin paste. S4. Finally, after curing with visible blue light of wavelength 400-500 nm for 30-180 seconds, a non-releasing antibacterial dental light-curing composite resin is obtained.

4. The method for preparing the non-release antibacterial dental light-curing composite resin according to claim 3, characterized in that: The preparation method of the non-release inorganic composite guanidine salt polymer antibacterial agent in step S2 comprises the following steps: S10. Add epoxy functionalized silica, guanidine polymer, polyether polyol and methyl silicone oil to a kneader with an ultrasonic generator, pass inert gas protection at normal pressure, start stirring at room temperature to mix the materials evenly, then increase the temperature and stir to melt the polymer material and mix it evenly with the epoxy functionalized silica, at the same time, start the kneader ultrasonic generator, under the action of ultrasonic waves, promote the epoxy functionalized silica to be fully dispersed in the molten material for reaction, and maintain the reaction temperature of 100 to 200° C. for 1 to 8 hours, then, maintain the original reaction temperature of the kneader, the agitator and the ultrasonic generator, turn off the inert gas, vacuum degas for 1 to 3 hours, pass inert gas to normal pressure, add zinc ricinoleate, and continue stirring for 0.5 to 2 hours under the protection of inert gas; S11. After the reaction in step S10 is completed, the molten product is cooled to room temperature, and then the cooled solid product is crushed into powder; S12. The crushed product of step S11 is then dispersed in distilled water to form a suspension, the solid product is separated by filtration, and then washed with an organic solvent. The separated solid product is then dried and crushed into powder to prepare a non-release inorganic composite guanidine salt polymer antibacterial agent.

5. The method for preparing the non-release antibacterial dental light-curing composite resin according to claim 4, characterized in that: The organic solvent in step S12 is selected from methanol, ethanol or acetone, and the inert gas in step S10 is nitrogen or argon.

6. A preparation device for the preparation method according to claim 4 or 5, characterized in that: including an ultrasonic kneading component; The ultrasonic kneading component is provided with a cylinder body, multiple groups of ultrasonic generators, inert pipe fittings and vacuum pipe fittings. The cylinder body is provided with a feeding port, and the feeding port is provided with a sealing cover body. Multiple groups of ultrasonic generators are arranged on the side of the cylinder body. The inert pipe fittings are installed on the cylinder body and used to pass inert gas in or out. The vacuum pipe fittings are installed on the cylinder body and used to extract air in the cylinder body. Control valves are installed on the inert pipe fittings and the vacuum pipe fittings respectively. The frequencies of the multiple groups of ultrasonic generators are respectively set to 20kHz, and the power adjustment range of a single ultrasonic generator in the multiple groups of ultrasonic generators is 0 to 500W.

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