Dental light-cured composite resin with long-acting antibacterial property and preparation method of dental light-cured composite resin

Abstract

The invention relates to the technical field of polymer composite materials, in particular to long-acting antibacterial dental light-cured composite resin and a preparation method thereof. According to the specific technical scheme, the long-acting antibacterial dental light-cured composite resin is prepared from the following components in parts by weight: 40 to 60 parts of acrylate prepolymer, 20 to 50 parts of acrylate monomer, 1 to 5 parts of photoinitiator, 2 to 10 parts of inorganic filler and 0.1 to 10 parts of antibacterial additive. The dental light-cured composite resin with the long-acting antibacterial property, prepared by the preparation method disclosed by the invention, has the safety and the aesthetic property while improving the antibacterial and anti-caries effects.

Description

Technical Field

[0001] This invention relates to the field of polymer composite materials technology, specifically to a dental light-cured composite resin with long-lasting antibacterial properties and its preparation method, which is suitable for dental medical scenarios requiring high antibacterial durability. Background Technology

[0002] Traditional dental restoration fabrication relies on manual molding and casting, which suffers from low precision, long production cycles, and significant patient discomfort, and also makes personalized customization difficult. With the development of digital healthcare, 3D printing technology, with its layer-by-layer material deposition characteristics, provides a precise and efficient solution for dental restorations. Photopolymerization 3D printing technology selectively cures photosensitive resin using ultraviolet light, allowing for layer-by-layer deposition and minimizing errors to the micrometer level. This reduces the production cycle to 1-3 days, significantly improving restoration efficiency and precision.

[0003] However, traditional light-cured composite resin restorations are prone to secondary caries and marginal microleakage, allowing bacteria to invade the restoration-tooth interface and cause infection, significantly reducing the lifespan of the restoration. While traditional light-cured resins can improve mechanical properties and aesthetics, they lack active antibacterial function and are difficult to inhibit cariogenic bacteria. In dental restorative materials, caries recurrence and periodontal infection are prominent issues. Traditional antibacterial agents struggle to achieve a "repair-prevention dual function" and are prone to drug resistance or disruption of the oral microecology. Therefore, there is an urgent need to develop safe and long-lasting antibacterial dental restorative resins.

[0004] Currently, nanocomposite materials have become an important development direction for dental antibacterial agents due to their high specific surface area and sustained-release properties. For example, Chinese patent CN111110572A uses zinc-doped mesoporous silica microspheres as an antibacterial agent added to the matrix resin, utilizing the slow release of the antibacterial component Zn from the mesoporous silica. 2+ This method aims to achieve antibacterial properties. However, it has the following drawbacks: ① Poor antibacterial durability: Untreated antibacterial agents are prone to migration or precipitation, leading to long-term antibacterial failure; ② Decreased mechanical properties: High amounts of antibacterial agents may damage the resin matrix structure and reduce material strength; ③ Increased biosafety risks: Some antibacterial agents may cause cytotoxicity if released too quickly in the initial stage.

[0005] This invention uses silica as a carrier and integrates the dual effects of silver ions and fluoride ions through nanotechnology to prepare an inorganic nano-antibacterial agent with silver and fluoride co-load. When added to a photocurable resin prepolymer, it can improve the antibacterial and anti-caries effect while taking into account safety and aesthetics. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention provides a dental light-cured composite resin with long-lasting antibacterial properties and its preparation method, which improves antibacterial and anti-caries effects while also ensuring safety and aesthetics.

[0007] To achieve the above objectives, the present invention provides the following technical solution:

[0008] This invention discloses a dental light-cured composite resin with long-lasting antibacterial properties, comprising the following components by weight:

[0009] The composition includes 40-60 parts of acrylate prepolymer, 20-50 parts of acrylate monomers, 1-5 parts of photoinitiator, 2-10 parts of inorganic filler, and 0.1-10 parts of antibacterial additive.

[0010] Preferably, the acrylate prepolymer is one or more of the following: aliphatic polyurethane monoacrylate oligomer, aliphatic polyurethane hexaacrylate, aliphatic polyurethane diacrylate, epoxy acrylate oligomer, and polyester acrylate oligomer.

[0011] Preferably, the acrylate monomer is one or more of acrylamide morpholine, cyclotrihydroxymethylpropane methyl acetal acrylate, tricyclodecanediethanol diacrylate, 1,6-hexanediol diacrylate, tri(2-hydroxyethyl)isocyanurate triacrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated glycerol triacrylate.

[0012] Preferably, the photoinitiator is a pyrolysis initiator, and is one or more of 2,4,6-trimethylbenzoyl-xylphosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, and 1-hydroxy-cyclohexyl-phenyl ketone;

[0013] The inorganic filler is a nano-gas phase powder with a particle size of 12-40 nm, including one or more of nano-calcium carbonate, nano-gas phase alumina, and nano-gas phase titanium dioxide.

[0014] Preferably, the antibacterial additive is a silica-supported silver-fluorine composite.

[0015] Preferably, the size of the silica-supported silver-fluorine composite is 80-120 nm, Ag + The loading capacity is 60-80 mg / g, F - The loading capacity is 5-7 mg / g.

[0016] Preferably, the preparation of the silica-supported silver-fluorine composite includes the following steps:

[0017] S1. Preparation of dendritic silica

[0018] Modified silica was prepared using tetraethyl orthosilicate as the silicon source via a W / S / O microemulsion system.

[0019] S2, Preparation of silica-supported silver-fluorine composite

[0020] SiO2 was immersed in a 0.1 mol / L AlCl3 solution and reacted at 60-80℃ and 100-300 rpm for 2-4 hours. After the reaction was completed, Al-SiO2 support powder was obtained. Al-SiO2 was dispersed in an ethanol / water mixture containing AgNO3 and NaF and reacted with shaking at 40-50℃ for 3-5 hours. After the reaction was completed, the final reaction product, a silica-supported silver-fluorine composite, was obtained.

[0021] Preferably, in step S1, the mass ratio of W phase, S phase, and O phase in the W / S / O microemulsion system is 6.0:0.8:9.0-9.0:1.5:6.0; wherein, W phase: template agent, 0.4 mol / L urea aqueous solution; S phase: surfactant, composed of m 正丁醇 :m 十六烷基三甲基溴化铵 = 1:1 composition; O phase: cyclohexane; the molar ratio of tetraethyl orthosilicate to 0.4 mol / L urea aqueous solution is 1:1.5-1:2.5.

[0022] Preferably, in step S1, the W phase, S phase and O phase are mixed and stirred at 1000-1200 rpm for 0.5-1 h at room temperature to form a uniform and transparent microemulsion system; tetraethyl orthosilicate is slowly added to the microemulsion system at a rate of 1-3 drops / s; after the addition is completed, the temperature is raised to 60-80℃ and the reaction is kept at a constant temperature for 12-24 h; after drying, it is calcined at 600℃ for 6-12 h to obtain porous SiO2 powder.

[0023] Correspondingly, a method for preparing a dental light-cured composite resin with long-lasting antibacterial properties involves adding a photoinitiator to an acrylate monomer and mixing it, then adding an inorganic filler and an antibacterial additive, continuing to mix and stir, then adding an acrylate prepolymer, mixing, and then vacuum degassing to obtain a dental light-cured composite resin with long-lasting antibacterial properties.

[0024] The present invention has the following beneficial effects:

[0025] (1) Compared with traditional single antibacterial modes, the composite resin material prepared in this invention can exert synergistic antibacterial and anti-caries effects. Its mechanism of action is as follows: Ag + Broad-spectrum bactericidal effect is achieved by interfering with the synthesis of pathogenic cell walls, destroying protein structure and genetic material; F - It promotes enamel remineralization, seals dentinal tubules, and enhances the teeth's resistance to acid erosion, reducing the risk of caries from the source; the combination of the two can simultaneously block bacterial colonization and demineralization processes, improving the efficacy of caries prevention.

[0026] (2) Using porous silica as a carrier can ensure the controlled release of silver ions and fluorides, and the antibacterial effect can last for weeks to months, reducing the need for frequent application.

[0027] (3)SiO2@(Ag-F) is an inorganic nanoparticle that is easy to disperse uniformly in the resin system and does not affect the photocuring process. Moreover, the introduction of nanoparticles will further enhance the mechanical strength of the resin material.

[0028] (4) The inorganic material matrix (silver, fluorine, and silicon dioxide) introduced in the preparation process of this invention is non-toxic, non-irritating, and does not induce bacterial drug resistance. The prepared resin has good biocompatibility and can be applied to the field of dental restoration. Attached Figure Description

[0029] Figure 1 SEM image of the dendritic mesoporous silica prepared in Example 1;

[0030] Figure 2 TEM image of SiO2@(Ag-F) prepared in Example 1;

[0031] Figure 3 The results of the effect of composite resin 1 on the viability of L-929 cells by the MTT assay are shown in (a) blank control group, (b) positive control group, (c) negative control group and (d) 100% composite resin 1 extract. Detailed Implementation

[0032] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0033] Unless otherwise specified, the technical means used in the implementation examples are conventional means well known to those skilled in the art.

[0034] This invention discloses a dental light-cured composite resin with long-lasting antibacterial properties, comprising the following components by weight:

[0035] The composition includes 40-60 parts of acrylate prepolymer, 20-50 parts of acrylate monomers, 1-5 parts of photoinitiator, 2-10 parts of inorganic filler, and 0.1-10 parts of antibacterial additive.

[0036] The acrylate prepolymer is one or more of the following: aliphatic polyurethane monoacrylate oligomer (PUA), aliphatic polyurethane hexaacrylate (APPA), aliphatic polyurethane diacrylate (FPUA), epoxy acrylate oligomer (EA), and polyester acrylate oligomer (PEA).

[0037] The acrylate monomers are one or more of the following: acrylamide (ACMO), cyclotrimethylolpropane methyl acetal acrylate (CTFA), tricyclodecanediethanol diacrylate (DCPDA), 1,6-hexanediol diacrylate (HDDA), tri(2-hydroxyethyl)isocyanurate triacrylate (THEICTA), ethoxylated trimethylolpropane triacrylate (TMP3EOTA), and propoxylated glycerol triacrylate (G3.5POTA).

[0038] The photoinitiator is a pyrolysis initiator, and is one or more of 2,4,6-trimethylbenzoyl-xylylphosphine oxide (TMO), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone (907), and 1-hydroxy-cyclohexyl-phenyl ketone (184);

[0039] The inorganic filler is a nano-gas phase powder with a particle size of 12-40 nm, including one or more of nano-calcium carbonate (CaCO3), nano-gas phase alumina (Al2O3), and nano-gas phase titanium dioxide (TiO2).

[0040] The antibacterial additive is a silica-supported silver-fluorine composite (SiO2@(Ag-F)). The silica-supported silver-fluorine composite has a size of 80-120 nm, and Ag... + The loading capacity is 60-80 mg / g, F - The loading capacity is 5-7 mg / g.

[0041] Furthermore, the preparation of the silica-supported silver-fluorine composite includes the following steps:

[0042] S1. Preparation of dendritic silica

[0043] Modified silica was prepared using tetraethyl orthosilicate (TEOS) as the silicon source via a W / S / O microemulsion system (W phase, S phase, and O phase mass ratio 6.0:0.8:9.0-9.0:1.5:6.0); wherein the W phase was a template agent, a 0.4 mol / L urea aqueous solution; and the S phase was a surfactant, composed of m... 正丁醇 :m 十六烷基三甲基溴化铵 = 1:1 composition; O phase: cyclohexane; the molar ratio of tetraethyl orthosilicate to 0.4 mol / L urea aqueous solution is 1:1.5-1:2.5.

[0044] The specific preparation process is as follows:

[0045] In a container equipped with a stirrer and a temperature measuring device, n-butanol, hexadecyltrimethylammonium bromide, urea aqueous solution, and cyclohexane were added sequentially. The mixture was mechanically stirred at 1000-1200 rpm for 0.5-1 h at room temperature to form a homogeneous and transparent microemulsion system. TEOS was weighed and transferred to a constant-pressure dropping funnel, and slowly added dropwise to the microemulsion system at a rate of 1-3 drops / second. After the addition was complete, a reflux condenser was installed, and the temperature was raised to 60-80℃ and maintained for 12-24 h. The reaction product was washed three times by centrifugation with anhydrous ethanol, vacuum dried at 60℃ for 6 h, and then transferred to a muffle furnace for calcination at 600℃ for 6-12 h to obtain porous SiO2 powder.

[0046] S2, Preparation of silica-supported silver-fluorine composite

[0047] Through Al 3+ Fluorine coordination sites are constructed on the SiO2 surface by doping, while Ag is adsorbed using residual oxygen groups. + Specifically: Dissolve aluminum chloride (AlCl3) in anhydrous ethanol to prepare a 0.1 mol / L AlCl3 solution. Immerse SiO2 in the 0.1 mol / L AlCl3 solution. Place the mixture in a constant temperature shaker at 60-80℃ and react at 100-300 rpm for 2-4 hours. After the reaction is complete, wash the mixture with anhydrous ethanol at least three times by centrifugation, dry it under vacuum at 60℃ for 6-12 hours, and then centrifuge and wash again to obtain Al-SiO2 support powder. The mass-to-volume ratio of SiO2 to AlCl3 solution is 1:25-35.

[0048] Al-SiO2 was dispersed in an ethanol / water mixture containing AgNO3 (0.1 mol / L) and NaF (0.2 mol / L) (V AgNO 3:V NaF The mixture of Al-SiO2 and AgNO3 / NaF solutions was reacted at a constant temperature of 1-4:1-2 (1-4:1-2) for 3-5 hours with constant temperature shaking. After the reaction was complete, the mixture was washed at least three times with anhydrous ethanol by centrifugation and then dried under vacuum at 60°C for 6-12 hours to obtain the final product SiO2@(Ag-F). Different loadings of SiO2@(Ag-F) could be obtained by adjusting the volume ratio of AgNO3 to NaF solution. The mass-volume ratio of Al-SiO2 to the AgNO3 and NaF mixture was 1:15-25.

[0049] This invention discloses a method for preparing a dental photocurable composite resin with long-lasting antibacterial properties. The method involves adding a photoinitiator to an acrylate monomer and mixing it, then adding an inorganic filler and an antibacterial additive (SiO2@(Ag-F)), continuing to mix and stir, then adding an acrylate prepolymer, mixing, and then vacuum degassing to obtain a dental photocurable composite resin with long-lasting antibacterial properties.

[0050] The present invention will be further described below with reference to specific embodiments.

[0051] Example 1: Preparation of Composite Resin 1

[0052] 1. The preparation steps of SiO2@(Ag-F) are as follows:

[0053] (1) In a container equipped with a stirrer and a temperature measuring device, n-butanol (6.25 g), hexadecyltrimethylammonium bromide (CTAB, 6.25 g), 0.4 mol / L urea aqueous solution (93.75 mL), and cyclohexane (93.75 g) were added sequentially. The mixture was mechanically stirred at 1200 rpm for 30 min at 25 °C to form a homogeneous and transparent microemulsion system. TEOS (5.2 g) was weighed and transferred to a constant-pressure dropping funnel, and slowly added dropwise to the microemulsion system at a rate of 1-3 drops / second. After the addition was complete, a reflux condenser was installed, the temperature was raised to 70 °C, and the reaction was maintained at this temperature for 24 h. The reaction product was washed three times by centrifugation with anhydrous ethanol, vacuum dried at 60 °C for 6 h, and then transferred to a muffle furnace and calcined at 600 °C for 6 h to obtain porous SiO2 powder. Its SEM image is shown below. Figure 1 As shown, dendritic porous SiO2 was successfully prepared.

[0054] (2) Immerse 3.0g SiO2 in 0.1mol / L AlCl3 (100mL) solution, place the mixture in an 80℃ constant temperature shaker, and react at 200rpm for 2h. After the reaction is complete, wash with anhydrous ethanol more than 3 times by centrifugation, dry under vacuum at 60℃ for 6h, and centrifuge to obtain Al-SiO2 support powder.

[0055] (3) Disperse Al-SiO2 (5g) in 100mL (V) of an ethanol / water mixture containing AgNO3 (0.1mol / L) and NaF (0.2mol / L). AgNO 3:V NaF =3:2), the reaction was carried out at 40℃ with constant shaking for 3 hours. After the reaction was completed, the product was washed more than 3 times with anhydrous ethanol by centrifugation, and then dried under vacuum at 60℃ for 6 hours to obtain the target reaction product SiO2@(Ag-F). Its TEM image is shown below. Figure 2 As shown, the results indicate that the SiO2 support still maintains a porous network structure with uniform pore size distribution. After aluminum modification, the pore walls are strengthened without collapse. Within the silica channels, silver is embedded in the channels as high-brightness isolated particles, appearing as speckled dispersions.

[0056] 2. Preparation of composite resin 1

[0057] Weigh 3 parts of 2,4,6-trimethylbenzoyl-xylphosphine oxide and add them to a mixture of 34 parts of acryloyloxymorpholine and 5 parts of tricyclodecanediethanol diacrylate. After mixing at room temperature, add 1 part of the above-synthesized SiO2@(Ag-F) nanoparticles, 5 parts of fumed alumina and 5 parts of nano-calcium carbonate and continue mixing until homogeneous. Then add 30 parts of aliphatic polyurethane monoacrylate and 17 parts of aliphatic polyurethane diacrylate, mix well and degas under vacuum to obtain composite resin 1.

[0058] Example 2: Preparation of Composite Resin 2

[0059] The preparation process of SiO2@(Ag-F) is the same as in Example 1.

[0060] The preparation process of composite resin 2 is as follows: 3 parts of 2,4,6-trimethylbenzoyl-xylphosphine oxide were weighed and added to a mixture of 34 parts of cyclotrihydroxymethylpropane methyl acetal acrylate and 5 parts of 1,6-hexanediol diacrylate. After mixing at room temperature, 1 part of SiO2@(Ag-F) nanoparticles synthesized in Example 1, 5 parts of fumed alumina and 5 parts of nano-calcium carbonate were added and mixed evenly. Then, 30 parts of aliphatic polyurethane monoacrylate and 17 parts of aliphatic polyurethane hexaacrylate were added, mixed evenly, and vacuum degassed to obtain composite resin 2.

[0061] Example 3: Preparation of Composite Resin 3

[0062] The preparation process of SiO2@(Ag-F) is the same as in Example 1.

[0063] The preparation process of composite resin 3 is as follows: 3 parts of 2,4,6-trimethylbenzoyl-xylphosphine oxide were weighed and added to a mixture of 17 parts of cyclotrihydroxymethylpropane methyl acetal acrylate, 18 parts of acryloyloxymorpholine and 5 parts of tri(2-hydroxyethyl)isocyanurate triacrylate. After mixing at room temperature, 1 part of SiO2@(Ag-F) nanoparticles synthesized in Example 1, 5 parts of fumed alumina and 5 parts of nano-calcium carbonate were added and mixed evenly. Then, 30 parts of aliphatic polyurethane diacrylate and 17 parts of aliphatic polyurethane hexaacrylate were added, mixed evenly, and vacuum degassed to obtain composite resin 3.

[0064] Preparation of composite resin 4 in Comparative Example 1

[0065] Unlike Example 1, only 47 parts of aliphatic polyurethane hexaacrylate were added in the preparation of the composite resin.

[0066] Preparation of composite resin 5 in Comparative Example 2

[0067] Unlike Example 1, only 47 parts of aliphatic polyurethane diacrylate were added in the preparation of the composite resin.

[0068] Preparation of composite resin 6 in Comparative Example 3

[0069] Unlike Example 1, only 47 parts of aliphatic polyurethane monoacrylate were added in the preparation of the composite resin.

[0070] Preparation of composite resin 7 in Comparative Example 4

[0071] Unlike Example 1, in the synthesis of SiO2@(Ag-F), the volume ratio of AgNO3 solution to NaF solution was 4:1.

[0072] Preparation of composite resin 8 in Comparative Example 5

[0073] Unlike Example 1, in the synthesis of SiO2@(Ag-F), the volume ratio of AgNO3 solution to NaF solution was 1:1.

[0074] Preparation of composite resin 9 in Comparative Example 6

[0075] Unlike Example 1, the mass of the support Al-SiO2 in the synthesis of SiO2@(Ag-F) was 4g.

[0076] Preparation of composite resin 10 in Comparative Example 7

[0077] Unlike Example 1, the mass of the support Al-SiO2 in the synthesis of SiO2@(Ag-F) was 6g.

[0078] Preparation of composite resin 11 in Comparative Example 8

[0079] Unlike Example 1, SiO2@(Ag-F) is not added to the composite resin.

[0080] Preparation of composite resin 12 in Comparative Example 9

[0081] Unlike Example 1, 0.5 parts of SiO2@(Ag-F) were added to the composite resin.

[0082] Preparation of composite resin 13 in Comparative Example 10

[0083] Unlike Example 1, 1.5 parts of SiO2@(Ag-F) were added to the composite resin.

[0084] Example 4 Performance Test

[0085] Mechanical property testing: The composite resins prepared in each embodiment and comparative example were cured into standard test samples using an LCD printer or DLP printer, and their performance was tested using the following methods:

[0086] Hardness: Measured according to ASTM D 2240;

[0087] Tensile properties: determined according to GB / T 1040.1-2018;

[0088] Bending performance: Tested in accordance with GB / T 9341-2008;

[0089] Impact strength: determined according to ASTM D D256;

[0090] Antibacterial activity: Referring to GB / T 31402-2023, the immediate and long-term antibacterial effects of composite resin 1-12 against *Escherichia coli* (ATCC 8739) were evaluated. After the initial test, samples from the same batch were immersed in physiological saline and placed in a 37℃ constant temperature water bath shaking chamber, and tested again on days 30, 60, and 90.

[0091] Cytotoxicity test: The composite resin 1 was tested according to GB / T 16886.5-2017. The negative control group was high-density polyethylene (HDPE), and the positive control group was polyurethane (0.1% ZDEC).

[0092] The results of the mechanical property test are shown in Table 1, the results of the antibacterial property test are shown in Table 2, and the results of the cytotoxicity test are shown in Table 3.

[0093] Table 1 Performance test results of the examples and comparative examples

[0094]

[0095]

[0096] As shown in Table 1, the performance test results of composite resins 1-6 indicate that adding aliphatic polyurethane hexaacrylate or aliphatic polyurethane diacrylate alone can improve the rigidity of the material, but it will make the material brittle and reduce its impact resistance. Since polyurethane hexaacrylate contains a hexafunctional structure, it can impart a higher crosslinking density, while aliphatic polyurethane acrylate has high flexibility and strong impact resistance. Combining the two can balance flexibility and rigidity, thus improving the mechanical properties of the material.

[0097] From the performance test results of composite resins 1 and 7-10 in Table 1, it can be seen that when the mass of the support Al-SiO2 is 5g and the volume ratio of AgNO3 solution to NaF solution is 3:2, the Ag... + With F - With balanced loading, the Ag-F synergistic effect was significant, resulting in the highest antibacterial rate. When the volume ratio of AgNO3 solution to NaF solution was 4:1, Ag... + The load is the highest due to high Ag. + The ratio promotes uniform distribution of nanoparticles, but at this time F -The load is relatively low, mainly Ag + Sustained release of dominant antibacterial activity; when the volume ratio of AgNO3 solution to NaF solution is 1:1, Ag... + Low load, F - High loading and competitive adsorption can lead to poor nanoparticle dispersion. - Its antibacterial contribution is limited. Maintaining a 3:2 volume ratio of AgNO3 solution to NaF solution, and with a carrier Al-SiO2 mass of 4g, compared to SiO2@(Ag-F) in composite resin 1, the AgNO3 solution at this point... + and F - The loading was slightly lower, resulting in a relatively lower antibacterial rate; when the mass of the Al-SiO2 carrier was 6g, the Ag content was lower. + The load is the lowest, F - The load is high, the synergistic effect between the two is poor, and the antibacterial properties are low.

[0098] As shown in Table 1, the performance test results of composite resins 1 and 11-13 indicate that the amount of SiO2@(Ag-F) nanoparticles added not only affects the antibacterial effect but also the mechanical properties. When the addition amount is 0.5 parts, the Ag content at low addition levels... + The release rate is relatively slow, and the antibacterial effect is mainly through contact sterilization. - The synergistic effect is relatively weak; when the addition amount is 1 part, the synergistic effect of Ag-F is enhanced, achieving highly efficient antibacterial activity by disrupting bacterial cell membranes and interfering with metabolism; further increasing the addition amount of SiO2@(Ag-F) and the concentration of Ag + Continuous release, combined with F - The osmotic pressure effect causes bacteria to die rapidly, but the addition of Ag-F nanoparticles will enhance the cross-linking density and matrix rigidity, which will reduce the impact resistance of the material.

[0099] Table 2. Long-term antibacterial performance test results of the examples and comparative examples.

[0100]

[0101] Table 2 shows that the addition of SiO2@(Ag-F) enhances the antibacterial effect of the composite resin, reducing secondary caries and extending the lifespan of the restoration by inhibiting bacterial growth. On one hand, Ag... + Ag achieves broad-spectrum bactericidal effects by interfering with pathogen cell wall synthesis, disrupting protein structure and genetic material. + After killing bacteria, it detaches from the bacterial cell and repeatedly acts on other bacteria, achieving long-lasting antibacterial effects; on the other hand, F -It promotes enamel remineralization, seals dentinal tubules, and enhances teeth's resistance to acid erosion, reducing the risk of caries from the source; the combination of these two methods can simultaneously block bacterial colonization and demineralization processes, improving caries prevention efficacy. The high specific surface area and controllable pore size of the mesoporous SiO2 carrier enable uniform loading of silver nanoparticles, preventing aggregation and enhancing Ag... + Release stability.

[0102] Table 3. Cytotoxicity test results of composite resin 1

[0103] Group Cell survival percentage Potential cytotoxicity 100% Composite Resin Extract 108.16％ No potential cytotoxicity 75% Composite Resin Extract 107.55％ No potential cytotoxicity 50% Composite Resin Extract 99.77％ No potential cytotoxicity 25% Composite Resin Extract 88.21％ No potential cytotoxicity Positive control group 3.21％ Meets requirements negative control group 88.22％ Meets requirements Blank control group - -

[0104] Figure 3 These are the morphological observation results for each group in Table 3. Figure 3 (d) is a 100% extract of composite resin 1. After 24 hours of contact, the cell density of the 100% composite resin 1 extract is approximately 100%. The cells are spindle-shaped or extended, adherent to the wall, with a few round cells located in the second layer. There are discrete granules in the cytoplasm, no cell lysis, and no decrease in cell proliferation. The preparation processes of composite resin 1, positive control group, negative control group, and blank control group are shown in Tables 4 and 5.

[0105] The data in Table 3 clearly show that the 100% extract of the composite resin has no potential cytotoxicity to L-929 cells. The negative control group, HDPE, showed no significant toxicity to L-929 cells, meeting the biocompatibility requirements. The purpose of the negative control group was to verify the reliability of the experimental system and eliminate false positive results. The positive control group, containing ZDEC-containing polyurethane, exhibited strong cytotoxicity, leading to almost complete death of L-929 cells, consistent with the expected effect of the positive control. This demonstrates that the composite resin prepared in this invention has good biocompatibility and is suitable for dental restoration.

[0106] Table 4. Preparation of extracts from composite resin 1 and negative control group.

[0107]

[0108]

[0109] Table 5. Preparation of extracts from the blank control group and the positive control group

[0110]

[0111] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A dental light-cured composite resin with long-lasting antibacterial properties, characterized in that: Based on parts by weight, it includes the following components: The composition includes 40-60 parts of acrylate prepolymer, 20-50 parts of acrylate monomers, 1-5 parts of photoinitiator, 2-10 parts of inorganic filler, and 0.1-10 parts of antibacterial additive.

2. The dental light-cured composite resin with long-lasting antibacterial properties according to claim 1, characterized in that: The acrylate prepolymer is one or more of the following: aliphatic polyurethane monoacrylate oligomer, aliphatic polyurethane hexaacrylate, aliphatic polyurethane diacrylate, epoxy acrylate oligomer, and polyester acrylate oligomer.

3. The dental light-cured composite resin with long-lasting antibacterial properties according to claim 1, characterized in that: The acrylate monomers are one or more of acrylamide morpholine, cyclotrihydroxymethylpropane methyl acetal acrylate, tricyclodecanediethanol diacrylate, 1,6-hexanediol diacrylate, tri(2-hydroxyethyl)isocyanurate triacrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated glycerol triacrylate.

4. The dental light-cured composite resin with long-lasting antibacterial properties according to claim 1, characterized in that: The photoinitiator is a cleavage-type initiator, and is one or more of 2,4,6-trimethylbenzoyl-xylphosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, and 1-hydroxy-cyclohexyl-phenyl ketone; The inorganic filler is a nano-gas phase powder with a particle size of 12-40 nm, including one or more of nano-calcium carbonate, nano-gas phase alumina, and nano-gas phase titanium dioxide.

5. A dental light-cured composite resin with long-lasting antibacterial properties according to any one of claims 1-4, characterized in that: The antibacterial additive is a silica-supported silver-fluorine complex.

6. The dental light-cured composite resin with long-lasting antibacterial properties according to claim 5, characterized in that: The silica-supported silver-fluorine composite has a size of 80-120 nm, Ag + The loading capacity is 60-80 mg / g, F - The loading capacity is 5-7 mg / g.

7. A dental light-cured composite resin with long-lasting antibacterial properties according to claim 5 or 6, characterized in that: The preparation of the silica-supported silver-fluorine composite includes the following steps: S1. Preparation of dendritic silica Modified silica was prepared using tetraethyl orthosilicate as the silicon source via a W / S / O microemulsion system. S2, Preparation of silica-supported silver-fluorine composite SiO2 was immersed in a 0.1 mol / L AlCl3 solution and reacted at 60-80℃ and 100-300 rpm for 2-4 hours. After the reaction was completed, Al-SiO2 support powder was obtained. Al-SiO2 was dispersed in an ethanol / water mixture containing AgNO3 and NaF and reacted with shaking at 40-50℃ for 3-5 hours. After the reaction was completed, the final reaction product, a silica-supported silver-fluorine composite, was obtained.

8. The dental light-cured composite resin with long-lasting antibacterial properties according to claim 7, characterized in that: In step S1, the mass ratio of W phase, S phase, and O phase in the W / S / O microemulsion system is 6.0:0.8:9.0-9.0:1.5:6.0; wherein, W phase: template agent, 0.4 mol / L urea aqueous solution; S phase: surfactant, composed of m 正丁醇 :m 十六烷基三甲基溴化铵 = 1:1 composition; O phase: cyclohexane; the molar ratio of tetraethyl orthosilicate to 0.4 mol / L urea aqueous solution is 1:1.5-1:2.

5.

9. The dental light-cured composite resin with long-lasting antibacterial properties according to claim 8, characterized in that: In step S1, the W phase, S phase and O phase are mixed and stirred at 1000-1200 rpm for 0.5-1 h at room temperature to form a uniform and transparent microemulsion system. Tetraethyl orthosilicate is slowly added to the microemulsion system at a rate of 1-3 drops / s. After the addition is completed, the temperature is raised to 60-80℃ and the reaction is kept at a constant temperature for 12-24 h. After drying, it is calcined at 600℃ for 6-12 h to obtain porous SiO2 powder.

10. A method for preparing a dental light-cured composite resin with long-lasting antibacterial properties as described in any one of claims 1-9, characterized in that: After adding the photoinitiator to the acrylate monomer and mixing it, inorganic fillers and antibacterial additives are added. After further mixing and stirring, acrylate prepolymer is added, and after mixing, vacuum degassing is performed to obtain a dental photocurable composite resin with long-lasting antibacterial properties.

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