Dental restorative composite material with antibacterial function

Abstract

The application belongs to the field of dental prosthetic materials, and particularly relates to a dental prosthetic composite material containing antibacterial function and a preparation method thereof. The dental prosthetic composite material containing antibacterial function comprises the following raw materials in parts by weight: modified filler 60-80 parts, modified bisphenol A-glycidyl methacrylate 14-25 parts, urethane dimethacrylate glycidyl 2-4 parts, triethylene glycol dimethacrylate 2.4-9.4 parts, antibacterial monomer 0.5-1 part, and photoinitiator 0.5-2 parts. The operation is carried out in the dark, the materials are mixed in proportion, uniformly stirred, and then discharged to obtain the dental prosthetic composite material containing antibacterial function. The dental prosthetic composite material containing antibacterial function solves the problems such as shrinkage, water absorption and bacterial growth in the prior art, and has excellent mechanical properties.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of dental restorative materials, and particularly relates to a dental restorative composite material containing antibacterial function. BACKGROUND

[0002] In recent years, resin-based dental composite resins have gradually become an important material for treating caries due to their aesthetic color, convenient operation, superior physicochemical and biological properties, and a series of advantages. Due to the complexity of the oral environment, the phenomenon of microleakage between the dental restorative material and the tooth itself and fracture inevitably occur during long-term service, thereby causing secondary caries and ultimately leading to repair failure. Therefore, to meet the clinical needs, the repair material should have excellent mechanical properties and good antibacterial properties.

[0003] Firstly, the root cause of secondary caries is the volume shrinkage of organic monomers in the repair material during double bond polymerization, forming a cavity. The most common solution is to increase the molecular weight of the linear monomer, increase the molecular volume, and reduce the density of the monomer double bond. However, this method also brings new problems such as high viscosity of the system, low filling amount, and poor operability. Bisphenol A-glycidyl methacrylate is the most commonly used basic resin in dental restorative materials so far, which has excellent mechanical properties, biocompatibility, and chemical stability. However, due to the presence of 2 hydroxyl groups in the molecular structure, hydrogen bonds are easily formed between molecules, which also leads to the biggest disadvantage of too high viscosity (1.0-1.2 kPa·s at 23℃). In order to increase the addition amount of inorganic fillers in the composite resin, diluents must be added to reduce the viscosity of the resin base (too much diluent also has the problem of increased volume shrinkage). The presence of hydroxyl groups also leads to high water absorption, which increases the solubility of the composite material. Therefore, the modification of bisphenol A-glycidyl methacrylate is also one of the key works.

[0004] In addition, the antibacterial property of dental restorative materials has attracted more and more attention. At present, the dental restorative materials with antibacterial properties mainly add antibacterial agents directly into the enhanced inorganic fillers to prepare high-strength dental restorative materials with antibacterial properties. For example, the patent CN106038322A selects mesoporous SiO2-coated antibacterial particles and silane-modified SiO2 as co-filler to give the composite resin good mechanical properties and antibacterial properties. However, the two particles in the composite material prepared by this method are only physically mixed, and there is no chemical bond interaction between them. Therefore, the antibacterial particles are prone to agglomeration and have a low filling amount, which limits the improvement of the antibacterial property of the repair material to a certain extent. SUMMARY

[0005] The tooth repair composite material with antibacterial function and the preparation method thereof are provided to solve the problems of shrinkage, water absorption and bacterial growth of the tooth repair material in the prior art.

[0006] To achieve the above object, the technical scheme adopted by the present application to solve its technical problems is:

[0007] The tooth repair composite material with antibacterial function comprises the following raw materials in parts by weight:

[0008] Modified filler 60-80 parts;

[0009] Modified bisphenol A-glycidyl methacrylate 14-25 parts;

[0010] Urethane dimethacrylate 2-4 parts;

[0011] Triethylene glycol dimethacrylate 2.4-9.4 parts;

[0012] Antibacterial monomer 0.5-1 part;

[0013] Photoinitiator 0.5-2 parts.

[0014] Preferably, the modified filler is prepared by the following method:

[0015] The silica is placed in a round-bottom flask, and then KH570 and cyclohexane A are added under magnetic stirring at room temperature for 30 min, and then heated and stirred in an oil bath at 60-70 DEG C for 2-4 h; after the reaction is completed, filtration is performed, the insoluble substance is washed with cyclohexane B and anhydrous ethanol for 3 times, and then dried in a vacuum oven at 40 DEG C for 24 h to obtain the modified filler;

[0016] The amount ratio of the silica, KH560, cyclohexane A, cyclohexane B and anhydrous ethanol is 10 g:0.5-1.5 g:100 mL:300 mL:400 mL.

[0017] Preferably, the average particle sizes of the silica are 1 μm and 50 nm respectively, and the mixture of the micron-sized silica and the nano-sized silica is in a mass ratio of 3-4:1.

[0018] Preferably, the modified bisphenol A-glycidyl methacrylate is prepared by the following method:

[0019] The fluorinated alkyl acyl chloride, dichloromethane A, bisphenol A-glycidyl methacrylate, triethylamine, dichloromethane B, saturated brine, saturated sodium bicarbonate solution, deionized water are used in a ratio of 1.2 mmol: 100 mL: 0.5 mmol: 1.2 mmol: 300 mL: 500 mL: 500 mL: 500 mL.

[0020] The fluorinated alkyl acyl chloride, dichloromethane A, bisphenol A-glycidyl methacrylate, triethylamine, dichloromethane B, saturated brine, saturated sodium bicarbonate solution, deionized water are used in a ratio of 1.2 mmol: 100 mL: 0.5 mmol: 1.2 mmol: 300 mL: 500 mL: 500 mL: 500 mL.

[0021] As a preferred, the fluorinated alkyl acyl chloride is perfluorobutyryl chloride, nonafluoropentanoyl chloride, perfluorooctanoyl chloride or heptadecafluorooctanoyl chloride.

[0022] As a preferred, the antibacterial monomer is prepared by the following method:

[0023] The biguanide derivative, glycidyl methacrylate, p-benzene diol, N, N-dimethyl formamide are added to a three-necked flask, stirred, heated to 40-60℃ for 3-6h, then distilled under reduced pressure, and dried in a vacuum oven at 40℃ for 24h to obtain the antibacterial monomer.

[0024] The biguanide derivative, glycidyl methacrylate, N, N-dimethyl formamide are used in a ratio of 0.5 mmol: 0.55 mmol: 400 mL.

[0025] The p-benzene diol is used in an amount of 0.05wt% of the glycidyl methacrylate.

[0026] As a preferred, the biguanide derivative is 1, 10-diguanidyl decane or polyhexamethylene guanidine.

[0027] As a preferred, the photoinitiator is a mixture of camphorquinone and 4-ethane-N, N-dimethyl amino benzoic acid ethyl ester.

[0028] A preparation method of a dental restorative composite material with antibacterial function, comprising the following steps:

[0029] The modified filler, modified bisphenol A-glycidyl methacrylate, urethane glycidyl dimethacrylate, triethylene glycol dimethacrylate, antibacterial monomer are mixed in proportion, a photoinitiator is added, stirred uniformly, and then discharged to obtain the dental restorative composite material with antibacterial function.

[0030] The present application has the following advantages:

[0031] (1) The present application provides a dental restorative composite material with antibacterial function, which uses modified fillers compared with traditional inorganic fillers. First, the nanoscale and microscale silica are used in combination, the nanoscale silica provides excellent wear resistance and compressive strength, and the microscale silica provides lower shrinkage, and the combination can effectively improve the overall performance; second, the chemical modification of the filler can effectively disperse the nanomaterials and improve the mechanical properties; at the same time, it can be fully wetted and coated with the matrix resin to avoid the existence of holes; third, the modified filler has an acryloxy structure, which can fully react with the matrix resin to form a strong bonding force at the organic-inorganic interface.

[0032] (2) The present application provides a dental restorative composite material with antibacterial function, which uses fluorinated modified bisphenol A-glycidyl methacrylate. First, the modified structure does not contain hydroxyl groups, which greatly reduces or even eliminates the formation of hydrogen bonds, effectively reducing the viscosity of the resin, thereby reducing the amount of diluent, and achieving the effect of reducing the polymerization shrinkage of the composite material; second, the modified structure also contains a large amount of F elements, which can be enriched on the surface of the material, and has a large hydrophobicity; at the same time, the F-containing surface effectively inhibits the growth and reproduction of bacteria.

[0033] (3) The present application provides a dental restorative composite material with antibacterial function, which uses a self-made antibacterial monomer. The monomer structure contains a guanidine group structure with a spectrum of antibacterial properties, which has high-efficiency and broad-spectrum antibacterial properties, and is fixed in the polymer network by forming a covalent bond with the modified filler or the matrix resin, and will not be released from the material, and has excellent antibacterial activity and durability before and after the curing of the composite material. DETAILED DESCRIPTION

[0034] The present application will be described in detail below in conjunction with the examples. However, it should be understood that the following examples are only illustrative of the embodiments of the present application, and are not a limitation on the scope of the present application.

[0035] The silica described in the following examples in the present application: micron-sized silica (SS-1, particle size distribution 0.4-1.5 μm, average particle size 1 μm) was purchased from Zhejiang Tongdawei Peng Electrical Co., Ltd.; nanoscale silica (CY-SP50, average particle size 50 nm) was purchased from Hangzhou Jiupeng New Material Co., Ltd.

[0036] Example 1

[0037] A dental restorative composite material with antibacterial function comprises the following raw materials in parts by weight:

[0038] Modified filler 70 parts;

[0039] Modified bisphenol A-glycidyl methacrylate 20 parts;

[0040] Urethane dimethacrylate glycidyl 3 parts;

[0041] Triethylene glycol dimethacrylate 5.4 parts;

[0042] Antibacterial monomer 0.6 parts;

[0043] Photoinitiator (camphorquinone and 4-ethane-N,N-dimethylamino ethyl benzoate in a mass ratio of 1:3.6) 1 part.

[0044] The above modified filler is prepared by the following method:

[0045] In the dark, silica (micron-sized silica and nanometer-sized silica in a mass ratio of 3.7:1) is placed in a round-bottom flask, KH570, cyclohexane A is added in turn, and magnetic stirring is carried out at room temperature for 30 min, and then heating stirring is carried out in an oil bath at 65℃ for 3 h; after the reaction is completed, filtration is carried out, the insoluble substance is washed with cyclohexane B and anhydrous ethanol for 3 times, and then drying is carried out in a vacuum oven at 40℃ for 24 h to obtain the modified filler;

[0046] The amount ratio of the silica, KH560, cyclohexane A, cyclohexane B and anhydrous ethanol is 10 g:1.0 g:100 mL:300 mL:400 mL.

[0047] Its infrared data are as follows: 3433 cm -1 :-OH exists; 1091 cm -1 :-Si-O-Si- exists; 1720 cm -1 :-C=O exists; 1614 cm -1 , 811 cm -1 :-C=C- exists.

[0048] The above modified bisphenol A-glycidyl methacrylate is prepared by the following method:

[0049] In the dark, heptadecafluorononanoyl chloride and dichloromethane A are dissolved in a constant-pressure dropping funnel, and then added dropwise into a round-bottom flask containing bisphenol A-glycidyl methacrylate, triethylamine and dichloromethane B, magnetic stirring is carried out, ice bath is carried out at 5℃, and after reaction for 10 h; standing, stirring overnight, filtration, washing the filtrate with saturated brine, saturated sodium bicarbonate solution and deionized water for 3 times respectively, separation, taking the organic phase, vacuum distillation at 40℃, and drying in a vacuum oven for 24 h to obtain the modified bisphenol A-glycidyl methacrylate;

[0050] The amount ratio of the seventeen fluorononyl chloride, dichloromethane A, bisphenol A-glycidyl methacrylate, triethylamine, dichloromethane B, saturated brine, saturated sodium bicarbonate solution, deionized water is: 1.2mmol: 100mL: 0.5mmol: 1.2mmol: 300mL: 500mL: 500mL: 500mL.

[0051] Its infrared data are as follows: 3550cm -1 : -OH disappears; 1720cm -1 : -C=O exists; 1614cm -1 , 811cm -1 : -C=C- exists. -1 : -C-F exists.

[0052] The above antibacterial monomer is prepared by the following method:

[0053] Polyhexamethylene guanidine (average molecular weight 15000), glycidyl methacrylate, hydroquinone, N,N-dimethylformamide are added to a three-necked flask, stirred, heated to 50℃ for 5h, then distilled under reduced pressure, and dried in a vacuum oven at 40℃ for 24h to obtain the antibacterial monomer;

[0054] The amount ratio of the polyhexamethylene guanidine, glycidyl methacrylate, N,N-dimethylformamide is: 0.5mmol: 0.55mmol: 400mL;

[0055] The amount of the hydroquinone is 0.05wt% of the amount of the glycidyl methacrylate.

[0056] Its infrared data are as follows: 3324cm -1 : -NH- sharp peak exists; 911cm -1 : epoxy group does not exist; 1654cm -1 : -C=N- exists; 1720cm -1 : -C=O exists; 1614cm -1 , 811cm -1 : -C=C- exists.

[0057] Example 2

[0058] An antibacterial functional dental repair composite material, comprising the following raw materials in parts by weight:

[0059] Modified filler 70 parts;

[0060] Modified bisphenol A-glycidyl methacrylate 20 parts;

[0061] Urethane dimethacrylate glycidyl 3 parts;

[0062] Triethylene glycol dimethacrylate 5.4 parts;

[0063] Antibacterial monomer 0.6 parts;

[0064] Photoinitiator (camphorquinone and 4-ethane-N,N-dimethylamino ethyl benzoate with a mass ratio of 1:3.6) 1 part.

[0065] The above modified filler is prepared by the following method:

[0066] In the dark, silica (micron-sized silica and nanometer-sized silica with a mass ratio of 3:1) is placed in a round-bottom flask, KH570 and cyclohexane A are added in sequence, and magnetic stirring is performed at room temperature for 30 min, and then heating stirring is performed in an oil bath at 60℃ for 4 h; after the reaction is completed, filtration is performed, the insoluble substance is washed with cyclohexane B and anhydrous ethanol for 3 times, and then drying is performed in a vacuum oven at 40℃ for 24 h to obtain the modified filler;

[0067] The amount ratio of the silica, KH560, cyclohexane A, cyclohexane B and anhydrous ethanol is 10 g:0.5 g:100 mL:300 mL:400 mL.

[0068] The infrared data are as follows: 3433 cm -1 :-OH exists; 1091 cm -1 :-Si-O-Si- exists; 1720 cm -1 :-C=O exists; 1614 cm -1 , 811 cm -1 :-C=C- exists.

[0069] The above modified bisphenol A-glycidyl methacrylate is prepared by the following method:

[0070] In the dark, perfluorobutyryl chloride and dichloromethane A are dissolved in a constant-pressure dropping funnel, and then added dropwise into a round-bottom flask containing bisphenol A-glycidyl methacrylate, triethylamine and dichloromethane B, magnetic stirring is performed, ice bath is performed at 0℃, and after reaction for 5 h; standing, stirring overnight, filtration, washing with saturated brine, saturated sodium bicarbonate solution and deionized water for 3 times respectively, separation, taking the organic phase, vacuum distillation at 40℃, and drying in a vacuum oven for 24 h to obtain the modified bisphenol A-glycidyl methacrylate;

[0071] The amount ratio of perfluorobutyryl chloride, dichloromethane A, bisphenol A-glycidyl methacrylate, triethylamine, dichloromethane B, saturated brine, saturated sodium bicarbonate solution and deionized water is 1.2 mmol:100 mL:0.5 mmol:1.2 mmol:300 mL:500 mL:500 mL:500 mL.

[0072] Its infrared data are as follows: 3550cm -1 : -OH disappears; 1720cm -1 : -C=O exists; 1614cm -1 , 811cm -1 : -C=C- exists. -1 : -C-F exists.

[0073] The antibacterial monomer is prepared by the following method:

[0074] Polyhexamethylene guanidine (average molecular weight 15000), glycidyl methacrylate, hydroquinone, N, N-dimethylformamide are added into a three-necked flask, stirred, heated to 60℃ for 4h, distilled under reduced pressure, and then dried in a vacuum oven at 40℃ for 24h to obtain the antibacterial monomer;

[0075] The polyhexamethylene guanidine, glycidyl methacrylate, N, N-dimethylformamide are used in a ratio of 0.5mmol: 0.55mmol: 400mL;

[0076] The hydroquinone is used in an amount of 0.05wt% of the amount of glycidyl methacrylate.

[0077] Its infrared data are as follows: 3324cm -1 : -NH- sharp peak exists; 911cm -1 : epoxy group does not exist; 1654cm -1 : -C=N- exists; 1720cm -1 : -C=O exists; 1614cm -1 , 811cm -1 : -C=C- exists.

[0078] Example 3

[0079] A dental restorative composite material containing antibacterial function comprises the following raw materials in parts by weight:

[0080] Modified filler 70 parts;

[0081] Modified bisphenol A-glycidyl methacrylate 20 parts;

[0082] Urethane dimethacrylate glycidyl 3 parts;

[0083] Triethylene glycol dimethacrylate 5.4 parts;

[0084] Antibacterial monomer 0.6 parts;

[0085] Photoinitiator (camphorquinone and 4-ethane-N, N-dimethylamino benzoic acid ethyl ester in a mass ratio of 1:3.6) 1 part.

[0086] The modified filler described above was prepared by the following method:

[0087] Protected from light, silica (micron-sized silica and nano-sized silica in a mass ratio of 4:1) was placed in a round-bottom flask, and KH570 and cyclohexane A were added successively. The mixture was magnetically stirred at room temperature for 30 min, and then heated and stirred in an oil bath at 70 °C for 2 h. After the reaction was completed, the mixture was filtered, and the insoluble matter was washed three times with cyclohexane B and anhydrous ethanol. The mixture was then dried in a vacuum oven at 40 °C for 24 h to obtain the modified filler.

[0088] The ratio of silicon dioxide, KH560, cyclohexane A, cyclohexane B, and anhydrous ethanol is 10g:1.5g:100mL:300mL:400mL.

[0089] Its infrared data is as follows: 3433cm -1 -OH is present; 1091 cm⁻¹ -1 -Si-O-Si- exists; 1720cm -1 -C=O exists; 1614cm -1 811cm -1 -C = C - exists.

[0090] The modified bisphenol A-glycidyl methacrylate described above is prepared by the following method:

[0091] Protected from light, perfluorooctanoyl chloride and dichloromethane A were dissolved in a constant pressure dropping funnel and added dropwise to a round-bottom flask containing bisphenol A-glycidyl methacrylate, triethylamine, and dichloromethane B. The mixture was magnetically stirred, placed in an ice bath, and reacted at 5°C for 10 hours. After standing and stirring overnight, the mixture was filtered, and the filtrate was washed three times with saturated saline solution and saturated sodium bicarbonate solution, and then washed three times with deionized water. The liquid was separated, and the organic phase was distilled under reduced pressure and dried in a vacuum oven at 40°C for 24 hours to obtain modified bisphenol A-glycidyl methacrylate.

[0092] The ratio of perfluorooctanoyl chloride, dichloromethane A, bisphenol A-glycidyl methacrylate, triethylamine, dichloromethane B, saturated saline solution, saturated sodium bicarbonate solution, and deionized water is 1.2 mmol: 100 mL: 0.5 mmol: 1.2 mmol: 300 mL: 500 mL: 500 mL: 500 mL.

[0093] Its infrared data is as follows: 3550cm -1 -OH disappears; 1720cm -1 -C=O exists; 1614cm -1 811cm -1 -C = C- exists; 1250cm-1 : -C-F exists.

[0094] The antibacterial monomer is prepared by the following method:

[0095] Polyhexamethylene guanidine (average molecular weight 15000), glycidyl methacrylate, hydroquinone, N, N-dimethylformamide are added into a three-necked flask, stirred, heated to 40℃ for 6h, distilled under reduced pressure, and then dried in a vacuum oven at 40℃ for 24h to obtain the antibacterial monomer;

[0096] The polyhexamethylene guanidine, glycidyl methacrylate, and N, N-dimethylformamide are used in a ratio of 0.5mmol: 0.55mmol: 400mL;

[0097] The hydroquinone is used in an amount of 0.05wt% of the amount of glycidyl methacrylate.

[0098] Its infrared data are as follows: 3324cm -1 : -NH- peak exists; 911cm -1 : epoxy group does not exist; 1654cm -1 : -C=N- exists; 1720cm -1 : -C=O exists; 1614cm -1 , 811cm -1 : -C=C- exists.

[0099] Example 4

[0100] A dental restorative composite material containing an antibacterial function comprises the following raw materials in parts by weight:

[0101] 70 parts of modified filler;

[0102] 20 parts of modified bisphenol A-glycidyl methacrylate;

[0103] 3 parts of urethane glycidyl dimethacrylate;

[0104] 5 parts of triethylene glycol dimethacrylate;

[0105] 1 part of antibacterial monomer;

[0106] 1 part of photoinitiator (camphorquinone and 4-ethane-N, N-dimethylamino benzoic acid ethyl ester in a mass ratio of 1:4).

[0107] The modified filler is prepared by the following method:

[0108] The silica (micron-sized silica and nano-sized silica in a mass ratio of 3.7:1) was placed in a round-bottom flask, and then KH570, cyclohexane A was added in sequence, and the mixture was stirred magnetically at room temperature for 30 min, and then heated and stirred in an oil bath at 60°C for 3 h; after the reaction was completed, the mixture was filtered, the insoluble substance was washed with cyclohexane B and anhydrous ethanol for 3 times, and then dried in a vacuum oven at 40°C for 24 h to obtain the modified filler.

[0109] The amount ratio of the silica, KH560, cyclohexane A, cyclohexane B and anhydrous ethanol is 10 g:1.0 g:100 mL:300 mL:400 mL.

[0110] The infrared data thereof are as follows: 3433 cm -1 :-OH exists; 1091 cm -1 :-Si-O-Si- exists; 1720 cm -1 :-C=O exists; 1614 cm -1 , 811 cm -1 :-C=C- exists.

[0111] The modified bisphenol A-glycidyl methacrylate is prepared by the following method:

[0112] The nonafluoropentanoyl chloride and dichloromethane A were dissolved in a constant-pressure dropping funnel, and then added dropwise into a round-bottom flask containing bisphenol A-glycidyl methacrylate, triethylamine and dichloromethane B, and the mixture was stirred magnetically in an ice bath at 0°C for 8 h; after standing, the mixture was stirred overnight, filtered, and the filtrate was washed with saturated brine, saturated sodium bicarbonate solution and deionized water for 3 times, respectively, and then separated, and the organic phase was distilled under reduced pressure, and dried in a vacuum oven at 40°C for 24 h to obtain the modified bisphenol A-glycidyl methacrylate.

[0113] The amount ratio of the nonafluoropentanoyl chloride, dichloromethane A, bisphenol A-glycidyl methacrylate, triethylamine, dichloromethane B, saturated brine, saturated sodium bicarbonate solution and deionized water is 1.2 mmol:100 mL:0.5 mmol:1.2 mmol:300 mL:500 mL:500 mL:500 mL.

[0114] The infrared data thereof are as follows: 3550 cm -1 :-OH disappears; 1720 cm -1 :-C=O exists; 1614 cm -1 , 811 cm -1 :-C=C- exists; 1250 cm -1 :-C-F exists.

[0115] The antibacterial monomer is prepared by the following method:

[0116] Polyhexamethylene guanidine (average molecular weight 15000), glycidyl methacrylate, hydroquinone, N,N-dimethyl formamide were added into a three-necked flask, stirred, heated to 60℃ for 5h, then distilled under reduced pressure, and dried in a vacuum oven at 40℃ for 24h to obtain the antibacterial monomer;

[0117] The ratio of polyhexamethylene guanidine, glycidyl methacrylate, N,N-dimethyl formamide was 0.5mmol:0.55mmol:400mL;

[0118] The amount of hydroquinone was 0.05wt% of the amount of glycidyl methacrylate.

[0119] Its infrared data were as follows: 3324cm -1 : -NH- peak existed; 911cm -1 : epoxy group did not exist; 1654cm -1 : -C=N- existed; 1720cm -1 : -C=O existed; 1614cm -1 , 811cm -1 : -C=C- existed.

[0120] Example 5

[0121] An antibacterial dental restoration composite material contained the following raw materials in parts by weight:

[0122] Modified filler 70 parts;

[0123] Modified bisphenol A-glycidyl methacrylate 20 parts;

[0124] Urethane glycidyl dimethacrylate 3 parts;

[0125] Triethylene glycol dimethacrylate 5.5 parts;

[0126] Antibacterial monomer 0.5 parts;

[0127] Photoinitiator (camphorquinone and 4-ethane-N,N-dimethylamino benzoic acid ethyl ester in a mass ratio of 1:3.5) 1 part.

[0128] The modified filler was prepared by the following method:

[0129] In the dark, silica (micron-sized silica and nanometer-sized silica in a mass ratio of 3.7:1) was placed in a round-bottom flask, KH570 and cyclohexane A were added in sequence, and magnetic stirring was performed at room temperature for 30min, and then heating and stirring were performed in an oil bath at 70℃ for 3h; after the reaction was completed, filtration was performed, the insoluble substance was washed with cyclohexane B and anhydrous ethanol for 3 times, and then drying was performed in a vacuum oven at 40℃ for 24h to obtain the modified filler.

[0130] The amount ratio of the silica, KH560, cyclohexane A, cyclohexane B, and anhydrous ethanol is 10g:1.0g:100mL:300mL:400mL.

[0131] Its infrared data are as follows: 3433cm -1 : -OH exists; 1091cm -1 : -Si-O-Si- exists; 1720cm -1 : -C=O exists; 1614cm -1 , 811cm -1 : -C=C- exists.

[0132] The modified bisphenol A-glycidyl methacrylate is prepared by the following method:

[0133] The heptadecafluorononanoyl chloride, dichloromethane A, bisphenol A-glycidyl methacrylate, triethylamine, dichloromethane B, saturated brine, saturated sodium bicarbonate solution, and deionized water are added to a constant pressure dropping funnel, and then added dropwise into a round-bottom flask containing the modified bisphenol A-glycidyl methacrylate, triethylamine, dichloromethane B, and saturated sodium bicarbonate solution, and then stirred magnetically in an ice bath at 0°C for 12h; after standing, the mixture is stirred overnight, filtered, and the filtrate is washed with saturated brine three times, washed with deionized water three times, separated, and the organic phase is distilled under reduced pressure, and then dried in a 40°C vacuum oven for 24h to obtain the modified bisphenol A-glycidyl methacrylate;

[0134] The amount ratio of the heptadecafluorononanoyl chloride, dichloromethane A, bisphenol A-glycidyl methacrylate, triethylamine, dichloromethane B, saturated brine, saturated sodium bicarbonate solution, and deionized water is 1.2mmol:100mL:0.5mmol:1.2mmol:300mL:500mL:500mL:500mL.

[0135] Its infrared data are as follows: 3550cm -1 : -OH disappears; 1720cm -1 : -C=O exists; 1614cm -1 , 811cm -1 : -C=C- exists; 1250cm -1 : -C-F exists.

[0136] The antibacterial monomer is prepared by the following method:

[0137] The 1,10-diguanidyl decane, glycidyl methacrylate, hydroquinone, and N,N-dimethylformamide are added to a three-necked flask, stirred, and then heated to 40°C for 4h, distilled under reduced pressure, and then dried in a 40°C vacuum oven for 24h to obtain the antibacterial monomer;

[0138] The amount ratio of the 1,10-diguanidyl decane, glycidyl methacrylate, N,N-dimethyl formamide is 0.5mmol:0.55mmol:400mL.

[0139] The amount of the hydroquinone is 0.05wt% of the amount of the glycidyl methacrylate.

[0140] Its infrared data are as follows: 3324cm -1 : -NH- peak exists; 911cm -1 : epoxy group does not exist; 1654cm -1 : -C=N- exists; 1720cm -1 : -C=O exists; 1614cm -1 , 811cm -1 : -C=C- exists.

[0141] Example 6

[0142] A dental restorative composite material with antibacterial function comprises the following raw materials in parts by weight:

[0143] Modified filler 60 parts;

[0144] Modified bisphenol A-glycidyl methacrylate 25 parts;

[0145] Urethane dimethacrylate glycidyl 4 parts;

[0146] Triethylene glycol dimethacrylate 9.4 parts;

[0147] Antibacterial monomer 0.6 parts;

[0148] Photoinitiator (camphorquinone and 4-ethane-N,N-dimethylamino benzoic acid ethyl ester in a mass ratio of 1:3.6) 1 part.

[0149] The above modified filler is prepared by the following method:

[0150] In the dark, silica (micron-sized silica and nanometer-sized silica in a mass ratio of 3.7:1) is placed in a round-bottom flask, KH570 and cyclohexane A are added successively, and magnetic stirring is carried out at room temperature for 30 min, and then heating and stirring are carried out in an oil bath at 65℃ for 3 h; after the reaction is completed, filtration is carried out, the insoluble substance is washed with cyclohexane B and anhydrous ethanol for 3 times, and then drying is carried out in a vacuum oven at 40℃ for 24 h to obtain the modified filler;

[0151] The amount ratio of the silica, KH560, cyclohexane A, cyclohexane B, anhydrous ethanol is 10g:1.0g:100mL:300mL:400mL.

[0152] Its infrared data are as follows: 3433cm-1 : -OH exists; 1091 cm -1 : -Si-O-Si- exists; 1720 cm -1 : -C=O exists; 1614 cm -1 , 811 cm -1 : -C=C- exists.

[0153] The modified bisphenol A-glycidyl methacrylate is prepared by the following method:

[0154] The perfluorooctanoyl chloride, dichloromethane A, bisphenol A-glycidyl methacrylate, triethylamine, dichloromethane B, saturated brine, saturated sodium bicarbonate solution, deionized water are added to a constant pressure dropping funnel, and are added dropwise to a round-bottom flask containing bisphenol A-glycidyl methacrylate, triethylamine, dichloromethane B, and are magnetically stirred, ice-bathed, and reacted at 0°C for 8h; after standing, stirring overnight, filtration, taking the filtrate, washing with saturated brine, saturated sodium bicarbonate solution 3 times, washing with deionized water 3 times, separating the liquid, taking the organic phase, reducing pressure distillation, drying in a 40°C vacuum oven for 24h, to obtain the modified bisphenol A-glycidyl methacrylate;

[0155] The perfluorooctanoyl chloride, dichloromethane A, bisphenol A-glycidyl methacrylate, triethylamine, dichloromethane B, saturated brine, saturated sodium bicarbonate solution, deionized water are added to a constant pressure dropping funnel, and are added dropwise to a round-bottom flask containing bisphenol A-glycidyl methacrylate, triethylamine, dichloromethane B, and are magnetically stirred, ice-bathed, and reacted at 0°C for 8h; after standing, stirring overnight, filtration, taking the filtrate, washing with saturated brine, saturated sodium bicarbonate solution 3 times, washing with deionized water 3 times, separating the liquid, taking the organic phase, reducing pressure distillation, drying in a 40°C vacuum oven for 24h, to obtain the modified bisphenol A-glycidyl methacrylate;

[0156] The infrared data are as follows: 3550 cm -1 : -OH disappears; 1720 cm -1 : -C=O exists; 1614 cm -1 , 811 cm -1 : -C=C- exists; 1250 cm -1 : -C-F exists.

[0157] The above-mentioned antibacterial monomer is prepared by the following method:

[0158] The 1,10-diguanidino decane, glycidyl methacrylate, hydroquinone, N,N-dimethyl formamide are added to a three-necked flask, stirred, heated to 50°C, reacted for 3h, reduced pressure distillation, dried in a 40°C vacuum oven for 24h, to obtain the antibacterial monomer;

[0159] The 1,10-diguanidino decane, glycidyl methacrylate, N,N-dimethyl formamide are added to a three-necked flask, stirred, heated to 50°C, reacted for 3h, reduced pressure distillation, dried in a 40°C vacuum oven for 24h, to obtain the antibacterial monomer;

[0160] The amount of hydroquinone is 0.05wt% of the amount of glycidyl methacrylate.

[0161] Its infrared data are as follows: 3324cm -1 : -NH- peak exists; 911cm -1 : epoxy group does not exist; 1654cm -1 : -C=N- exists; 1720cm -1 : -C=O exists; 1614cm -1 , 811cm -1 : -C=C- exists.

[0162] Example 7

[0163] An antibacterial dental restoration composite material comprises the following raw materials by weight:

[0164] Modified filler 80 parts;

[0165] Modified bisphenol A-glycidyl methacrylate 14 parts;

[0166] Urethane dimethacrylate glycidyl 2 parts;

[0167] Triethylene glycol dimethacrylate 2.4 parts;

[0168] Antibacterial monomer 0.6 parts;

[0169] Photoinitiator (camphorquinone and 4-ethane-N, N-dimethylamino benzoic acid ethyl ester in a mass ratio of 1:3.6) 1 part.

[0170] The above modified filler is prepared by the following method:

[0171] In the dark, silica (micron-sized silica and nanometer-sized silica in a mass ratio of 3.7:1) is placed in a round-bottom flask, KH570 and cyclohexane A are added in sequence, and magnetic stirring is performed at room temperature for 30 min, and then heating and stirring are performed in an oil bath at 65℃ for 3 h; after the reaction is completed, filtration is performed, the insoluble substance is washed with cyclohexane B and anhydrous ethanol for 3 times, and then drying is performed in a vacuum oven at 40℃ for 24 h to obtain the modified filler;

[0172] The amount ratio of the silica, KH560, cyclohexane A, cyclohexane B and anhydrous ethanol is 10g:1.0g:100mL:300mL:400mL.

[0173] Its infrared data are as follows: 3433cm -1 : -OH exists; 1091cm -1 : -Si-O-Si- exists; 1720cm -1 : -C=O exists; 1614cm -1 , 811cm -1 : -C=C- exists.

[0174] The modified bisphenol A-glycidyl methacrylate described above is prepared by the following method:

[0175] Protected from light, perfluorobutyryl chloride and dichloromethane A were dissolved in a constant pressure dropping funnel and added dropwise to a round-bottom flask containing bisphenol A-glycidyl methacrylate, triethylamine, and dichloromethane B. The mixture was magnetically stirred, placed in an ice bath, and reacted at 0°C for 8 hours. After standing and stirring overnight, the mixture was filtered, and the filtrate was washed three times with saturated saline solution and saturated sodium bicarbonate solution, and then washed three times with deionized water. The liquid was separated, and the organic phase was distilled under reduced pressure and dried in a vacuum oven at 40°C for 24 hours to obtain modified bisphenol A-glycidyl methacrylate.

[0176] The ratio of perfluorobutyroyl chloride, dichloromethane A, bisphenol A-glycidyl methacrylate, triethylamine, dichloromethane B, saturated saline solution, saturated sodium bicarbonate solution, and deionized water is 1.2 mmol: 100 mL: 0.5 mmol: 1.2 mmol: 300 mL: 500 mL: 500 mL: 500 mL.

[0177] Its infrared data is as follows: 3550cm -1 -OH disappears; 1720cm -1 -C=O exists; 1614cm -1 811cm -1 -C = C- exists; 1250cm -1 :-CF exists.

[0178] The above-mentioned antimicrobial monomers are prepared by the following method:

[0179] 1,10-diguanidinyldecane, glycidyl methacrylate, hydroquinone, and N,N-dimethylformyl were added to a three-necked flask, stirred, heated to 50°C and reacted for 4 hours, then distilled under reduced pressure and dried in a vacuum oven at 40°C for 24 hours to obtain the antibacterial monomer.

[0180] The ratio of 1,10-diguanidinyldecane, glycidyl methacrylate, and N,N-dimethylformamide is 0.5 mmol: 0.55 mmol: 400 mL.

[0181] The amount of hydroquinone used is 0.05 wt% of the amount of glycidyl methacrylate used.

[0182] Its infrared data is as follows: 3324cm -1 -NH- spike present; 911 cm⁻¹ -1 Epoxy groups are absent; 1654cm -1 -C=N- Exists; 1720cm -1 -C=O exists; 1614cm-1 , 811 cm -1 : -C=C- exists.

[0183] A dental restoration composite material with antibacterial function, a preparation method thereof, comprising the following steps:

[0184] In the dark, the modified filler, modified bisphenol A-glycidyl methacrylate, urethane dimethacrylate glycidyl, triethylene glycol dimethacrylate, and antibacterial monomer are mixed in proportion, and a photoinitiator is added. After stirring uniformly, the material is discharged to obtain a dental restoration composite material with antibacterial function.

[0185] The implementation examples 1-7 are compared with the implementation example 1:

[0186] Implementation example 1

[0187] A dental restoration composite material with antibacterial function, comprising the following raw materials in parts by weight:

[0188] Modified filler 70 parts;

[0189] Modified bisphenol A-glycidyl methacrylate 20 parts;

[0190] Urethane dimethacrylate glycidyl 3 parts;

[0191] Triethylene glycol dimethacrylate 5.4 parts;

[0192] Antibacterial monomer 0.6 parts;

[0193] Photoinitiator (camphorquinone and 4-ethane-N,N-dimethylaminoethyl benzoate in a mass ratio of 1:3.6) 1 part.

[0194] The above modified filler is prepared by the following method:

[0195] In the dark, micron-sized silicon dioxide is placed in a round-bottom flask, and KH570 and cyclohexane A are added in sequence. After magnetic stirring at room temperature for 30 min, heating and stirring are carried out at 65℃ in an oil bath for 3h. After the reaction is completed, filtration is carried out, and the insoluble substance is washed with cyclohexane B and anhydrous ethanol for 3 times. Then, drying is carried out in a vacuum oven at 40℃ for 24h to obtain the modified filler.

[0196] The amount ratio of the micron-sized silicon dioxide, KH560, cyclohexane A, cyclohexane B, and anhydrous ethanol is 10g:1.0g:100mL:300mL:400mL.

[0197] Its infrared data are as follows: 3433 cm -1 : -OH exists; 1091 cm -1 : -Si-O-Si- exists; 1720 cm-1 : -C=O exists; 1614 cm -1 , 811 cm -1 : -C=C- exists.

[0198] The preparation method of the modified bisphenol A-glycidyl methacrylate is the same as that in Embodiment 1.

[0199] The preparation method of the antibacterial monomer is the same as that in Embodiment 1.

[0200] Comparative Example 2

[0201] A dental restorative composite material with antibacterial function comprises the following raw materials in parts by weight:

[0202] Modified filler 70 parts;

[0203] Modified bisphenol A-glycidyl methacrylate 20 parts;

[0204] Urethane dimethacrylate glycidyl 3 parts;

[0205] Triethylene glycol dimethacrylate 5.4 parts;

[0206] Antibacterial monomer 0.6 parts;

[0207] Photoinitiator (camphorquinone and 4-ethane-N,N-dimethylamino ethyl benzoate in a mass ratio of 1:3.6) 1 part.

[0208] The modified filler is prepared by the following method:

[0209] In the dark, the nanoscale silicon dioxide is placed in a round-bottom flask, KH570 and cyclohexane A are added in sequence, and magnetic stirring is performed at room temperature for 30 min, and then heating and stirring are performed in an oil bath at 65°C for 3 h; after the reaction is completed, filtration is performed, the insoluble substance is washed with cyclohexane B and anhydrous ethanol for 3 times, and then drying is performed in a vacuum oven at 40°C for 24 h to obtain the modified filler;

[0210] The amount ratio of the nanoscale silicon dioxide, KH560, cyclohexane A, cyclohexane B and anhydrous ethanol is 10 g:1.0 g:100 mL:300 mL:400 mL.

[0211] Its infrared data are as follows: 3433 cm -1 : -OH exists; 1091 cm -1 : -Si-O-Si- exists; 1720 cm -1 : -C=O exists; 1614 cm -1 , 811 cm -1 : -C=C- exists.

[0212] The preparation method of the modified bisphenol A-glycidyl methacrylate is the same as that in Embodiment 1.

[0213] The preparation method of the antibacterial monomer is the same as that in Embodiment 1.

[0214] Comparative Example 3

[0215] A dental restorative composite material with antibacterial function comprises the following raw materials in parts by weight:

[0216] Silica (micron-sized silica and nano-sized silica at a mass ratio of 3.7:1) 70 parts;

[0217] Modified bisphenol A-glycidyl methacrylate 20 parts;

[0218] Urethane dimethacrylate glycidyl 3 parts;

[0219] Triethylene glycol dimethacrylate 5.4 parts;

[0220] Antibacterial monomer 0.6 parts;

[0221] Photoinitiator (camphorquinone and 4-ethane-N,N-dimethylamino benzoic acid ethyl ester at a mass ratio of 1:3.6) 1 part.

[0222] The preparation method of the modified bisphenol A-glycidyl methacrylate is the same as that in Embodiment 1.

[0223] The preparation method of the antibacterial monomer is the same as that in Embodiment 1.

[0224] Comparative Example 4

[0225] A dental restorative composite material with antibacterial function comprises the following raw materials in parts by weight:

[0226] Modified filler 70 parts;

[0227] Bisphenol A-glycidyl methacrylate 20 parts;

[0228] Urethane dimethacrylate glycidyl 3 parts;

[0229] Triethylene glycol dimethacrylate 5.4 parts;

[0230] Antibacterial monomer 0.6 parts;

[0231] Photoinitiator (camphorquinone and 4-ethane-N,N-dimethylamino benzoic acid ethyl ester at a mass ratio of 1:3.6) 1 part.

[0232] The preparation method of the modified filler is the same as that in Embodiment 1.

[0233] The preparation method of the above antibacterial monomer is the same as that in Specific Example 1.

[0234] Comparative Example 5

[0235] A dental restorative composite material with antibacterial properties, comprising the following raw materials in parts by weight:

[0236] 70 parts of modified filler;

[0237] 20 parts of modified bisphenol A-glycidyl methacrylate;

[0238] 3 parts of glycidyl dimethacrylate;

[0239] 6 parts of triethylene dimethacrylate;

[0240] 1 part of photoinitiator (camphorquinone and ethyl 4-ethane-N,N-dimethylaminobenzoate in a mass ratio of 1:3.6).

[0241] The preparation method of the modified filler is the same as in Specific Example 1.

[0242] The preparation method of the modified bisphenol A-glycidyl methacrylate is the same as in Specific Example 1.

[0243] The preparation method of the above antibacterial monomer is the same as that in Specific Example 1.

[0244] Comparative Example 6

[0245] A dental restorative composite material with antibacterial properties, comprising the following raw materials in parts by weight:

[0246] 70 parts of modified filler;

[0247] 20 parts of modified bisphenol A-glycidyl methacrylate;

[0248] 3 parts of glycidyl dimethacrylate;

[0249] 5.4 parts of triethylene glycol dimethacrylate;

[0250] 0.6 parts of polyhexamethylene guanidine (average molecular weight 15000);

[0251] 1 part of photoinitiator (camphorquinone and ethyl 4-ethane-N,N-dimethylaminobenzoate in a mass ratio of 1:3.6).

[0252] The preparation method of the modified filler is the same as in Specific Example 1.

[0253] The preparation method of the modified bisphenol A-glycidyl methacrylate is the same as in Specific Example 1.

[0254] Comparative Example 7

[0255] A dental restorative composite material with antibacterial properties, comprising the following raw materials in parts by weight:

[0256] 70 parts of modified filler;

[0257] 20 parts of modified bisphenol A-glycidyl methacrylate;

[0258] 3 parts of glycidyl dimethacrylate;

[0259] 5.4 parts of triethylene glycol dimethacrylate;

[0260] 0.6 parts of 1,10-diguanidinyldecane;

[0261] 1 part of photoinitiator (camphorquinone and ethyl 4-ethane-N,N-dimethylaminobenzoate in a mass ratio of 1:3.6).

[0262] The preparation method of the modified filler is the same as in Specific Example 1.

[0263] The preparation method of the modified bisphenol A-glycidyl methacrylate is the same as in Specific Example 1.

[0264] The preparation method of the antibacterial dental restorative material described in Comparative Examples 1-7 is the same as that in Specific Example 1.

[0265] Using the antibacterial dental restorative composite materials obtained in Specific Examples 1-7 and Comparative Examples 1-7 as base materials, the composite resin samples were placed in silicone rubber molds and cured for 10-200 seconds using a lamp with a wavelength of 410-500 nm. After demolding, composite resin samples were obtained. The samples were then stored at room temperature in the dark for 2-3 days. Before testing, the sample surface was sanded with silicon carbide sandpaper to remove the incompletely cured resin layer.

[0266] The physical properties of the dental restorative composite materials with antibacterial function prepared in Examples 1-7 and Comparative Examples 1-7 of the present invention were measured respectively, and the results are shown in Table 1.

[0267] Table 1 Physical test performance of each embodiment

[0268]

[0269]

[0270] First, as shown in Table 1, the dental restorative composite material with antibacterial function of the present invention exhibits excellent mechanical properties, low shrinkage, low water absorption, antibacterial properties, and durable antibacterial activity, as observed in Examples 1 and Comparative Examples 1-2. It can be observed that the use of nano- and micro-scale silica in a compound formulation effectively improves overall performance. Chemical modification of the filler in Examples 1 and Comparative Example 3 effectively wets and disperses nanomaterials, improving mechanical properties and reducing polymerization shrinkage. The composite material of the present invention exhibits low water absorption, low viscosity, and a high water contact angle, inhibiting growth and reproduction; furthermore, due to the presence of side groups, it also has a lower volume shrinkage rate. The composite material of the present invention exhibits excellent antibacterial properties and durable antibacterial activity, as shown in Examples 1 and Comparative Examples 5-7.

[0271] The testing method is as follows:

[0272] (1) Flexural strength and compressive strength: The preparation method and testing procedure for the mechanical properties of the composite resin samples were in accordance with ISO 4049-2009. The cured and demolded resin samples were sanded smooth with silicon carbide sandpaper and placed at room temperature for 72 hours. The flexural strength and compressive strength were tested using an electronic universal testing machine.

[0273] (2) Abrasion Resistance: Composite resin samples were prepared using stainless steel molds. The sample dimensions were 10 mm in diameter and 6 mm in height. The resin was cured in three layers, each 2 mm thick, for 40 seconds. Three samples were prepared for each formulation of composite resin. The cured samples were placed in deionized water at 37°C and cured in the dark for 24 hours. Abrasion resistance testing was then conducted according to industry standard YY / T0113-2015. After 150 abrasive pre-grinding cycles, the sample was removed, cleaned, dried, and weighed to obtain m1. Then, after 1500 abrasive rubbing cycles, the sample was removed, cleaned, dried, and weighed again to obtain m2. The sample density ρ was then measured. The volumetric abrasion loss of the composite resin (unit: mm) can then be calculated. 3 The abrasion rate of the composite resin for each formulation is the average of the test results of three samples.

[0274] Volumetric wear = (m2-m1) / ρ.

[0275] (3) Viscosity: The viscosity of the monomer was measured using a Hacker stress rheometer at a frequency range of 0.001-100 rad / s and a temperature of 25℃. The rotation speed was set to 10 rad / s.

[0276] (4) Water absorption rate: The resin was evenly filled into a Φ15mm×1mm silicone rubber mold, and both sides were irradiated with a curing lamp for 60s each. All sample discs were dried in a 37℃ oven for 48h, and then weighed using a balance until a stable mass m0 was obtained. The samples were then immersed in 37℃ deionized water for 7d, removed, and the excess water on the sample surface was wiped off with filter paper. The mass m1 was obtained by weighing. The water absorption rate (unit: ug / mm) can be calculated using the following formula. 3 ):

[0277] Water absorption rate = (m1-m0) / V×100%.

[0278] (5) Water contact angle: determined according to GB / T 30693-2014.

[0279] (6) Shrinkage rate: The polymerization shrinkage rate of the composite resin was tested in accordance with the international standard ISO 17304-2013. Based on Archimedes' principle, the mass of the composite resin in air and solution was measured by a density balance to obtain the density of the composite resin before and after curing, and then the polymerization shrinkage rate of the composite resin was calculated.

[0280] (7) Antibacterial rate: The antibacterial rate of dental composite resin was quantitatively analyzed according to the standard "ASTM E2180-07(2012)". After the initial test, the same batch of samples were immersed in deionized water and placed in a 37°C constant temperature water bath shaking box. The test was carried out again on the 15th day.

[0281] Based on the above-described preferred embodiments of the present invention, and through the foregoing description, those skilled in the art can make various changes and modifications without departing from the inventive concept. The technical scope of this invention is not limited to the contents of the specification, but must be determined according to the scope of the claims.

Claims

1. A dental restorative composite material with antibacterial function, characterized in that: The ingredients include the following parts by weight: 60-80 parts of modified filler; 14-25 parts of modified bisphenol A-glycidyl methacrylate; 2-4 parts of glycidyl dimethacrylate; 2.4-9.4 parts of triethylene dimethacrylate; Antibacterial monomer 0.5-1 part; Photoinitiator 0.5-2 parts; The modified filler is prepared by the following method: Protect from light, place silica in a round-bottom flask, add KH570 and cyclohexane A successively, and stir magnetically for 30 min at room temperature. Then heat and stir in an oil bath at 60-70℃ for 2-4 h. After the reaction is complete, filter, wash the insoluble matter three times with cyclohexane B and anhydrous ethanol, and then dry in a vacuum oven at 40℃ for 24 h to obtain the modified filler. The ratio of silica, KH560, cyclohexane A, cyclohexane B, and anhydrous ethanol is 10g: 0.5-1.5g: 100mL: 300mL: 400mL; The silica is a mixture of micron-sized silica and nano-sized silica; The modified bisphenol A-glycidyl methacrylate is prepared by the following method: Protected from light, fluoroalkyl acyl chloride and dichloromethane A were dissolved in a constant pressure dropping funnel and added dropwise to a round-bottom flask containing bisphenol A-glycidyl methacrylate, triethylamine, and dichloromethane B. The mixture was magnetically stirred, placed in an ice bath, and reacted at 0-5°C for 5-12 hours. After standing and stirring overnight, the mixture was filtered, and the filtrate was washed three times with saturated saline solution, three times with saturated sodium bicarbonate solution, and three times with deionized water. The liquid was separated, and the organic phase was distilled under reduced pressure and dried in a vacuum oven at 40°C for 24 hours to obtain modified bisphenol A-glycidyl methacrylate. The ratio of the following components is: fluoroalkyl acyl chloride, dichloromethane A, bisphenol A-glycidyl methacrylate, triethylamine, dichloromethane B, saturated saline solution, saturated sodium bicarbonate solution, and deionized water: 1.2 mmol: 100 mL: 0.5 mmol: 1.2 mmol: 300 mL: 500 mL: 500 mL: 500 mL. The antimicrobial monomer is prepared by the following method: Biguanide derivative, glycidyl methacrylate, hydroquinone, and N,N-dimethylformyl were added to a three-necked flask, stirred, and heated to 40-60℃ for 3-6 hours. The mixture was then distilled under reduced pressure and dried in a vacuum oven at 40℃ for 24 hours to obtain the antibacterial monomer. The ratio of the biguanidin derivative, glycidyl methacrylate, and N,N-dimethylformamide used is 0.5 mmol: 0.55 mmol: 400 mL. The amount of hydroquinone used is 0.05 wt% of the amount of glycidyl methacrylate used; The biguanide derivative is 1,10-bisguanyldecane or polyhexamethylene guanidine; The photoinitiator includes at least one of camphorquinone and ethyl 4-ethane-N,N-dimethylaminobenzoate.

2. The dental restorative composite material with antibacterial function according to claim 1, characterized in that: The silica has average particle sizes of 1 μm and 50 nm, and is a mixture of micron-sized silica and nano-sized silica in a mass ratio of 3-4:

1.

3. The dental restorative composite material with antibacterial function according to claim 1, characterized in that: The fluoroalkyl acyl chloride is perfluorobutyroyl chloride, nonafluoropentanoyl chloride, perfluorooctanoyl chloride, or heptadecafluorononanoyl chloride.

4. A method for preparing a dental restorative composite material with antibacterial function according to any one of claims 1-3, characterized in that: Includes the following steps: In the dark, the modified filler, modified bisphenol A-glycidyl methacrylate, urethane dimethacrylate, triethylene glycol dimethacrylate, and antibacterial monomer are mixed in proportion, a photoinitiator is added, and the mixture is stirred evenly before being discharged to obtain a dental restorative composite material with antibacterial function.

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