Antibacterial dental restorative material

Abstract

The application belongs to the field of dental restoration materials, and particularly relates to an antibacterial dental restoration material and a preparation method thereof. The antibacterial dental restoration material comprises the following raw materials in parts by weight: modified filler 60-80 parts, base resin 19-39 parts, 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 antibacterial dental restoration material. The antibacterial dental restoration material solves the problems of shrinkage, easy falling-off and easy breeding of bacteria of the dental restoration material in the prior art, and has excellent mechanical properties.

Description

Technical Field

[0001] This invention belongs to the field of dental restorative materials, specifically relating to an antibacterial dental restorative material. Background Technology

[0002] In recent years, dental caries, with its high incidence and wide range of occurrence, has received considerable attention due to its serious impact on patients' appearance and physical and mental health. Composite resin dental restorations have become the most commonly used restorative material in clinical practice due to their aesthetics, ease of use, and biocompatibility. However, extensive clinical practice has confirmed that composite resin is highly susceptible to secondary caries caused by material peeling or loss during its long-term use.

[0003] The root cause of secondary caries lies in the volume shrinkage that occurs during the polymerization of double bonds in the organic monomers of restorative materials, forming cavities. To address or reduce this polymerization shrinkage, a common method is to increase the molecular weight of linear monomers, increase molecular volume, and reduce the density of monomer double bonds. However, this method also introduces new problems such as high system viscosity, low filling capacity, and poor operability. In recent years, hyperbranched molecules, due to their larger molecular weight, relatively lower viscosity, and the structural characteristics of their peripheral multifunctional groups, have been introduced as novel organic monomers into the construction of dental restorative resin materials. Numerous studies have confirmed that the addition of hyperbranched molecules effectively reduces the polymerization shrinkage of restorative resin materials. Currently, this type of research mainly focuses on commercially available Boltron-type hyperbranched polyesters, which are limited to a single product and can only use corresponding single monomers, restricting their further development.

[0004] Furthermore, the antibacterial properties of dental restorative materials have received increasing attention. Currently, dental restorative materials with antibacterial properties are mainly prepared by directly adding antibacterial agents to reinforced inorganic fillers to create high-strength dental restorative materials with both antibacterial and antibacterial properties. For example, patent CN106038322A uses mesoporous SiO2-coated antibacterial particles and silane-modified SiO2 as co-fillers, giving the composite resin good flexural strength, flexural modulus, and antibacterial properties. However, in the composite material prepared by this method, the two particles are only physically mixed without chemical bonding. Therefore, the antibacterial particles are prone to agglomeration and the filling amount is low, which limits the improvement of the antibacterial properties of the restorative material.

[0005] Current research focuses on optimizing the strength properties of dental restorative resin materials by controlling the composition, morphology, particle size, and distribution of specific functional nanofillers, while there is little research on the low shrinkage and antibacterial properties of functional fillers. Summary of the Invention

[0006] The purpose of this invention is to address the problems of easy shrinkage, easy shedding, and easy bacterial growth in existing dental restorative materials by providing an antibacterial dental restorative material and its preparation method. By modifying the filler, a modified filler with a hyperbranched structure and antibacterial properties is synthesized as the main component. The composite material prepared by adding a matrix resin and an initiator effectively solves the above problems and also exhibits excellent mechanical properties.

[0007] To achieve the above objectives, the technical solution adopted by the present invention to solve its technical problem is as follows:

[0008] An antibacterial dental restorative material, comprising the following raw materials in parts by weight:

[0009] 60-80 parts of modified filler;

[0010] 19-39 parts of matrix resin;

[0011] Photoinitiator 0.5-2 parts.

[0012] Preferably, the modified filler is prepared by the following method:

[0013] (1) Place silica in a round-bottom flask, add KH560 and cyclohexane A one after another, stir magnetically for 30 min at room temperature, and then heat and stir in an oil bath at 60-70℃ for 2-4 h; after the reaction is completed, filter, wash the insoluble matter three times with cyclohexane B and anhydrous ethanol, and then dry in a vacuum oven at 65℃ for 24 h to obtain intermediate product I.

[0014] The ratio of silica, KH560, cyclohexane A, cyclohexane B, and anhydrous ethanol is 10g:0.1g:100mL:300mL:400mL;

[0015] (2) Place intermediate product I and N,N-dimethylformamide A in a round-bottom flask, stir, and use a peristaltic pump to dropwise add to a three-necked flask containing biguanide derivative and N,N-dimethylformamide B. Heat to 30-50℃ and react for 3-6 hours. Filter, rinse the insoluble matter three times with deionized water, and then dry in a vacuum oven at 65℃ for 24 hours to obtain intermediate product II.

[0016] The ratio of intermediate product I, N,N-dimethylformamide A, biguanide derivative, N,N-dimethylformamide B, and deionized water is 10.10 g : 100 mL : 0.45 mmol : 150 mL : 400 mL;

[0017] (3) Add intermediate product II, glycidyl methacrylate, hydroquinone, and N,N-dimethylformyl C to a three-necked flask, stir, heat to 40-60℃ and react for 3-6 hours, then distill under reduced pressure, filter, wash the insoluble matter three times with ethyl acetate, and then dry in a vacuum oven at 65℃ for 24 hours to obtain target product III.

[0018] The ratio of intermediate product II, glycidyl methacrylate, N,N-dimethylformamide C, and ethyl acetate is 10.179-10.208 g : 0.45 mmol : 200 mL : 400 mL;

[0019] The amount of hydroquinone used is 0.05 wt% of the amount of glycidyl methacrylate used.

[0020] Preferably, 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.

[0021] Preferably, the biguanide derivative is 1,5-diguanylpentane or 1,10-diguanyldecane.

[0022] Preferably, the matrix resin is a mixture of bisphenol A-glycidyl methacrylate, glycidyl urethane dimethacrylate, and triethylene glycol dimethacrylate.

[0023] Preferably, the photoinitiator is a mixture of camphorquinone and ethyl 4-ethane-N,N-dimethylaminobenzoate in a mass ratio of 1:2-4.

[0024] A method for preparing an antibacterial dental restorative material includes the following steps:

[0025] In the dark, the modified filler and matrix resin are mixed in proportion, a photoinitiator is added, and after stirring evenly, the material is discharged to obtain the antibacterial dental restoration material.

[0026] The present invention has the following beneficial effects:

[0027] This invention provides an antibacterial dental restorative material that uses a modified filler compared to traditional inorganic fillers. First, the silica is a blend of nano- and micro-scale silica. Nano-scale silica provides excellent wear resistance and compressive strength, while micro-scale silica provides lower shrinkage; the blend effectively improves overall performance. Second, chemical modification of the filler effectively disperses nanomaterials, improving mechanical properties; it also allows for thorough wetting and coating with the matrix resin, preventing pores. Third, the modified filler has an acryloyloxy structure, allowing for full reaction with the matrix resin and forming strong adhesion at the organic-inorganic interface. Fourth, the organic chain portion of the modified filler has a large molecular weight and chain length, and is a "quasi-hyperbranched structure," further reducing polymerization volume shrinkage. Fifth, the organic chain portion contains guanidine structures with spectral antibacterial properties, covalently fixed within the polymer network and not released from the material, exhibiting excellent antibacterial activity and durability both before and after the composite material cures. Detailed Implementation

[0028] The present invention will be described in detail below with reference to embodiments. However, it should be understood that the following embodiments are merely illustrative examples of implementation of the present invention and are not intended to limit the scope of the present invention.

[0029] The silica used in the following embodiments of the present invention is as follows: micron-sized silica (SS-1, particle size distribution 0.4-1.5μm, average particle size 1μm) was purchased from Zhejiang Tongda Weipeng Electric Co., Ltd.; nano-sized silica (CY-SP50, average particle size 50nm) was purchased from Hangzhou Jiupeng New Materials Co., Ltd.

[0030] Example 1

[0031] An antibacterial dental restorative material, comprising the following raw materials in parts by weight:

[0032] 70 parts of modified filler;

[0033] 14 parts of bisphenol A-glycidyl methacrylate;

[0034] Two parts of glycidyl dimethacrylate;

[0035] 13 parts of triethylene dimethacrylate;

[0036] 1 part of photoinitiator (camphorquinone and ethyl 4-ethane-N,N-dimethylaminobenzoate in a mass ratio of 1:3.6).

[0037] The modified filler described above was prepared by the following method:

[0038] (1) Place silica (micron-sized silica and nano-sized silica in a mass ratio of 3.7:1) in a round-bottom flask, add KH560 and cyclohexane A successively, stir magnetically for 30 min at room temperature, and then heat and stir in an oil bath at 65℃ for 3 h; after the reaction is completed, filter, wash the insoluble matter three times with cyclohexane B and anhydrous ethanol, and then dry in a vacuum oven at 65℃ for 24 h to obtain intermediate product I;

[0039] The ratio of silica, KH560, cyclohexane A, cyclohexane B, and anhydrous ethanol is 10g:0.1g:100mL:300mL:400mL;

[0040] Its infrared data is as follows: 3433cm -1 -OH is present; 1091 cm⁻¹ -1 -Si-O-Si- exists; 911cm -1 Epoxy groups are present.

[0041] (2) Place intermediate product I and N,N-dimethylformamide A in a round-bottom flask, stir, and use a peristaltic pump to dropwise add to a three-necked flask containing 1,10-diguanidinyldecane and N,N-dimethylformamide B. Heat to 40°C and react for 4 hours. Filter, rinse the insoluble matter three times with deionized water, and then dry in a vacuum oven at 65°C for 24 hours to obtain intermediate product II.

[0042] The ratio of intermediate product I, N,N-dimethylformamide A, 1,10-diguanidinyldecane, N,N-dimethylformamide B, and deionized water is 10.10 g : 100 mL : 0.45 mmol : 150 mL : 400 mL;

[0043] Its infrared data is as follows: 3300-3500cm -1 -OH and -NH- are present; 1091 cm⁻¹ -1 -Si-O-Si- exists; 911cm -1 Epoxy groups disappear; 1654cm -1 -C = N - Exists.

[0044] (3) Add intermediate product II, glycidyl methacrylate, hydroquinone, and N,N-dimethylformyl C to a three-necked flask, stir, heat to 50℃ and react for 5h, then distill under reduced pressure, filter, wash the insoluble matter three times with ethyl acetate, and then dry in a vacuum oven at 65℃ for 24h to obtain target product III.

[0045] The ratio of intermediate product II, glycidyl methacrylate, N,N-dimethylformamide C, and ethyl acetate is 10.208 g : 0.45 mmol : 200 mL : 400 mL.

[0046] The amount of hydroquinone used is 0.05 wt% of the amount of glycidyl methacrylate used;

[0047] Its infrared data is as follows: 3300-3500cm -1 -OH and -NH- are present; 1091 cm⁻¹ -1 -Si-O-Si- exists; 911cm -1 Epoxy groups are absent; 1654cm -1 -C=N- Exists; 1720cm -1 -C=O exists; 1611cm -1 811cm -1 -C = C - exists.

[0048] Example 2

[0049] An antibacterial dental restorative material, comprising the following raw materials in parts by weight:

[0050] 70 parts of modified filler;

[0051] 14 parts of bisphenol A-glycidyl methacrylate;

[0052] Two parts of glycidyl dimethacrylate;

[0053] 13 parts of triethylene dimethacrylate;

[0054] 1 part of photoinitiator (camphorquinone and ethyl 4-ethane-N,N-dimethylaminobenzoate in a mass ratio of 1:3.6).

[0055] The modified filler described above was prepared by the following method:

[0056] (1) Place silica (micron-sized silica and nano-sized silica in a mass ratio of 3:1) in a round-bottom flask, add KH560 and cyclohexane A successively, stir magnetically for 30 min at room temperature, and then heat and stir in an oil bath at 60℃ for 4 h; after the reaction is completed, filter, wash the insoluble matter three times with cyclohexane B and anhydrous ethanol, and then dry in a vacuum oven at 65℃ for 24 h to obtain intermediate product I;

[0057] The ratio of silica, KH560, cyclohexane A, cyclohexane B, and anhydrous ethanol is 10g:0.1g:100mL:300mL:400mL;

[0058] Its infrared data is as follows: 3433cm -1 -OH is present; 1091 cm⁻¹ -1 -Si-O-Si- exists; 911cm -1 Epoxy groups are present.

[0059] (2) Place intermediate product I and N,N-dimethylformamide A in a round-bottom flask, stir, and use a peristaltic pump to dropwise add to a three-necked flask containing 1,10-diguanidinyldecane and N,N-dimethylformamide B. Heat to 30°C and react for 6 hours. Filter, rinse the insoluble matter three times with deionized water, and then dry in a vacuum oven at 65°C for 24 hours to obtain intermediate product II.

[0060] The ratio of intermediate product I, N,N-dimethylformamide A, 1,10-diguanidinyldecane, N,N-dimethylformamide B, and deionized water is 10.10 g : 100 mL : 0.45 mmol : 150 mL : 400 mL;

[0061] Its infrared data is as follows: 3300-3500cm -1 -OH and -NH- are present; 1091 cm⁻¹ -1 -Si-O-Si- exists; 911cm -1 Epoxy groups disappear; 1654cm -1 :-C=N-exists.

[0062] (3) Add intermediate product II, glycidyl methacrylate, hydroquinone, and N,N-dimethylformyl C to a three-necked flask, stir, heat to 40℃ and react for 6 hours, then distill under reduced pressure, filter, wash the insoluble matter three times with ethyl acetate, and then dry in a vacuum oven at 65℃ for 24 hours to obtain target product III.

[0063] The ratio of intermediate product II, glycidyl methacrylate, N,N-dimethylformamide C, and ethyl acetate is 10.208 g : 0.45 mmol : 200 mL : 400 mL.

[0064] The amount of hydroquinone used is 0.05 wt% of the amount of glycidyl methacrylate used;

[0065] Its infrared data is as follows: 3300-3500cm -1 -OH and -NH- are present; 1091 cm⁻¹ -1 -Si-O-Si- exists; 911cm -1 Epoxy groups are absent; 1654cm -1 -C=N- Exists; 1720cm -1 -C=O exists; 1611cm -1 811cm -1 -C = C - exists.

[0066] Example 3

[0067] An antibacterial dental restorative material, comprising the following raw materials in parts by weight:

[0068] 70 parts of modified filler;

[0069] 14 parts of bisphenol A-glycidyl methacrylate;

[0070] Two parts of glycidyl dimethacrylate;

[0071] 13 parts of triethylene dimethacrylate;

[0072] 1 part of photoinitiator (camphorquinone and ethyl 4-ethane-N,N-dimethylaminobenzoate in a mass ratio of 1:3.6).

[0073] The modified filler described above was prepared by the following method:

[0074] (1) Place silica (micron-sized silica and nano-sized silica in a mass ratio of 4:1) in a round-bottom flask, add KH560 and cyclohexane A successively, stir magnetically for 30 min at room temperature, and then heat and stir in an oil bath at 70℃ for 2 h; after the reaction is completed, filter, wash the insoluble matter three times with cyclohexane B and anhydrous ethanol, and then dry in a vacuum oven at 65℃ for 24 h to obtain intermediate product I;

[0075] The ratio of silica, KH560, cyclohexane A, cyclohexane B, and anhydrous ethanol is 10g:0.1g:100mL:300mL:400mL;

[0076] Its infrared data is as follows: 3433cm -1 -OH is present; 1091 cm⁻¹ -1 -Si-O-Si- exists; 911cm -1 Epoxy groups are present.

[0077] (2) Place intermediate product I and N,N-dimethylformamide A in a round-bottom flask, stir, and use a peristaltic pump to dropwise add to a three-necked flask containing 1,10-diguanidinyldecane and N,N-dimethylformamide B. Heat to 50°C and react for 3 hours. Filter, rinse the insoluble matter three times with deionized water, and then dry in a vacuum oven at 65°C for 24 hours to obtain intermediate product II.

[0078] The ratio of intermediate product I, N,N-dimethylformamide A, 1,10-diguanidinyldecane, N,N-dimethylformamide B, and deionized water is 10.10 g : 100 mL : 0.45 mmol : 150 mL : 400 mL;

[0079] Its infrared data is as follows: 3300-3500cm -1 -OH and -NH- are present; 1091 cm⁻¹ -1-Si-O-Si- exists; 911cm -1 Epoxy groups disappear; 1654cm -1 :-C=N-exists.

[0080] (3) Add intermediate product II, glycidyl methacrylate, hydroquinone, and N,N-dimethylformyl C to a three-necked flask, stir, heat to 60℃ and react for 3 hours, then distill under reduced pressure, filter, wash the insoluble matter three times with ethyl acetate, and then dry in a vacuum oven at 65℃ for 24 hours to obtain target product III.

[0081] The ratio of intermediate product II, glycidyl methacrylate, N,N-dimethylformamide C, and ethyl acetate is 10.208 g : 0.45 mmol : 200 mL : 400 mL.

[0082] The amount of hydroquinone used is 0.05 wt% of the amount of glycidyl methacrylate used;

[0083] Its infrared data is as follows: 3300-3500cm -1 -OH and -NH- are present; 1091 cm⁻¹ -1 -Si-O-Si- exists; 911cm -1 Epoxy groups are absent; 1654cm -1 -C=N- Exists; 1720cm -1 -C=O exists; 1611cm -1 811cm -1 -C = C - exists.

[0084] Example 4

[0085] An antibacterial dental restorative material, comprising the following raw materials in parts by weight:

[0086] 70 parts of modified filler;

[0087] 14 parts of bisphenol A-glycidyl methacrylate;

[0088] Two parts of glycidyl dimethacrylate;

[0089] 13 parts of triethylene dimethacrylate;

[0090] 1 part of photoinitiator (camphorquinone and ethyl 4-ethane-N,N-dimethylaminobenzoate in a mass ratio of 1:4).

[0091] The modified filler described above was prepared by the following method:

[0092] (1) Place silica (micron-sized silica and nano-sized silica in a mass ratio of 3.7:1) in a round-bottom flask, add KH560 and cyclohexane A successively, stir magnetically for 30 min at room temperature, and then heat and stir in an oil bath at 65℃ for 3 h; after the reaction is completed, filter, wash the insoluble matter three times with cyclohexane B and anhydrous ethanol, and then dry in a vacuum oven at 65℃ for 24 h to obtain intermediate product I;

[0093] The ratio of silica, KH560, cyclohexane A, cyclohexane B, and anhydrous ethanol is 10g:0.1g:100mL:300mL:400mL;

[0094] Its infrared data is as follows: 3433cm -1 -OH is present; 1091 cm⁻¹ -1 -Si-O-Si- exists; 911cm -1 Epoxy groups are present.

[0095] (2) Place intermediate product I and N,N-dimethylformamide A in a round-bottom flask, stir, and use a peristaltic pump to dropwise add to a three-necked flask containing 1,10-diguanidinyldecane and N,N-dimethylformamide B. Heat to 40°C and react for 5 hours. Filter, rinse the insoluble matter three times with deionized water, and then dry in a vacuum oven at 65°C for 24 hours to obtain intermediate product II.

[0096] The ratio of intermediate product I, N,N-dimethylformamide A, 1,10-diguanidinyldecane, N,N-dimethylformamide B, and deionized water is 10.10 g : 100 mL : 0.45 mmol : 150 mL : 400 mL;

[0097] Its infrared data is as follows: 3300-3500cm -1 -OH and -NH- are present; 1091 cm⁻¹ -1 -Si-O-Si- exists; 911cm -1 Epoxy groups disappear; 1654cm -1 -C = N - Exists.

[0098] (3) Add intermediate product II, glycidyl methacrylate, hydroquinone, and N,N-dimethylformyl C to a three-necked flask, stir, heat to 50℃ and react for 5h, then distill under reduced pressure, filter, wash the insoluble matter three times with ethyl acetate, and then dry in a vacuum oven at 65℃ for 24h to obtain target product III.

[0099] The ratio of intermediate product II, glycidyl methacrylate, N,N-dimethylformamide C, and ethyl acetate is 10.208 g : 0.45 mmol : 200 mL : 400 mL.

[0100] The amount of hydroquinone used is 0.05 wt% of the amount of glycidyl methacrylate used;

[0101] Its infrared data is as follows: 3300-3500cm -1 -OH and -NH- are present; 1091 cm⁻¹ -1 -Si-O-Si- exists; 911cm -1 Epoxy groups are absent; 1654cm -1 -C=N- Exists; 1720cm -1 -C=O exists; 1611cm -1 811cm -1 -C = C - exists.

[0102] Example 5

[0103] An antibacterial dental restorative material, comprising the following raw materials in parts by weight:

[0104] 70 parts of modified filler;

[0105] 14 parts of bisphenol A-glycidyl methacrylate;

[0106] Two parts of glycidyl dimethacrylate;

[0107] 13 parts of triethylene dimethacrylate;

[0108] 1 part of photoinitiator (camphorquinone and ethyl 4-ethane-N,N-dimethylaminobenzoate in a mass ratio of 1:2).

[0109] The modified filler described above was prepared by the following method:

[0110] (1) Place silica (micron-sized silica and nano-sized silica in a mass ratio of 3.7:1) in a round-bottom flask, add KH560 and cyclohexane A successively, stir magnetically for 30 min at room temperature, and then heat and stir in an oil bath at 65℃ for 3 h; after the reaction is completed, filter, wash the insoluble matter three times with cyclohexane B and anhydrous ethanol, and then dry in a vacuum oven at 65℃ for 24 h to obtain intermediate product I;

[0111] The ratio of silica, KH560, cyclohexane A, cyclohexane B, and anhydrous ethanol is 10g:0.1g:100mL:300mL:400mL;

[0112] Its infrared data is as follows: 3433cm -1 -OH is present; 1091 cm⁻¹ -1 -Si-O-Si- exists; 911cm -1 Epoxy groups are present.

[0113] (2) Place intermediate product I and N,N-dimethylformamide A in a round-bottom flask, stir, and use a peristaltic pump to dropwise add to a three-necked flask containing 1,10-diguanidinyldecane and N,N-dimethylformamide B. Heat to 40°C and react for 4 hours. Filter, rinse the insoluble matter three times with deionized water, and then dry in a vacuum oven at 65°C for 24 hours to obtain intermediate product II.

[0114] The ratio of intermediate product I, N,N-dimethylformamide A, 1,10-diguanidinyldecane, N,N-dimethylformamide B, and deionized water is 10.10 g : 100 mL : 0.45 mmol : 150 mL : 400 mL;

[0115] Its infrared data is as follows: 3300-3500cm -1 -OH and -NH- are present; 1091 cm⁻¹ -1 -Si-O-Si- exists; 911cm -1 Epoxy groups disappear; 1654cm -1 -C = N - Exists.

[0116] (3) Add intermediate product II, glycidyl methacrylate, hydroquinone, and N,N-dimethylformyl C to a three-necked flask, stir, heat to 50℃ and react for 4 hours, then distill under reduced pressure, filter, wash the insoluble matter three times with ethyl acetate, and then dry in a vacuum oven at 65℃ for 24 hours to obtain target product III.

[0117] The ratio of intermediate product II, glycidyl methacrylate, N,N-dimethylformamide C, and ethyl acetate is 10.208 g : 0.45 mmol : 200 mL : 400 mL.

[0118] The amount of hydroquinone used is 0.05 wt% of the amount of glycidyl methacrylate used;

[0119] Its infrared data is as follows: 3300-3500cm -1 -OH and -NH- are present; 1091 cm⁻¹ -1 -Si-O-Si- exists; 911cm -1 Epoxy groups are absent; 1654cm -1 -C=N- Exists; 1720cm -1 -C=O exists; 1611cm -1 811cm -1 -C = C - exists.

[0120] Example 6

[0121] An antibacterial dental restorative material, comprising the following raw materials in parts by weight:

[0122] 60 parts of modified filler;

[0123] 19 parts of bisphenol A-glycidyl methacrylate;

[0124] 4 parts of glycidyl dimethacrylate;

[0125] 16 parts of triethylene dimethacrylate;

[0126] 1 part of photoinitiator (camphorquinone and ethyl 4-ethane-N,N-dimethylaminobenzoate in a mass ratio of 1:3.6).

[0127] The modified filler described above was prepared by the following method:

[0128] (1) Place silica (micron-sized silica and nano-sized silica in a mass ratio of 3.7:1) in a round-bottom flask, add KH560 and cyclohexane A successively, stir magnetically for 30 min at room temperature, and then heat and stir in an oil bath at 65℃ for 3 h; after the reaction is completed, filter, wash the insoluble matter three times with cyclohexane B and anhydrous ethanol, and then dry in a vacuum oven at 65℃ for 24 h to obtain intermediate product I;

[0129] The ratio of silica, KH560, cyclohexane A, cyclohexane B, and anhydrous ethanol is 10g:0.1g:100mL:300mL:400mL;

[0130] Its infrared data is as follows: 3433cm -1 -OH is present; 1091 cm⁻¹ -1 -Si-O-Si- exists; 911cm -1 Epoxy groups are present.

[0131] (2) Place intermediate product I and N,N-dimethylformamide A in a round-bottom flask, stir, and use a peristaltic pump to dropwise add to a three-necked flask containing 1,10-diguanidinyldecane and N,N-dimethylformamide B. Heat to 40°C and react for 4 hours. Filter, rinse the insoluble matter three times with deionized water, and then dry in a vacuum oven at 65°C for 24 hours to obtain intermediate product II.

[0132] The ratio of intermediate product I, N,N-dimethylformamide A, 1,10-diguanidinyldecane, N,N-dimethylformamide B, and deionized water is 10.10 g : 100 mL : 0.45 mmol : 150 mL : 400 mL;

[0133] Its infrared data is as follows: 3300-3500cm -1 -OH and -NH- are present; 1091 cm⁻¹ -1-Si-O-Si- exists; 911cm -1 Epoxy groups disappear; 1654cm -1 -C = N - Exists.

[0134] (3) Add intermediate product II, glycidyl methacrylate, hydroquinone, and N,N-dimethylformyl C to a three-necked flask, stir, heat to 50℃ and react for 5h, then distill under reduced pressure, filter, wash the insoluble matter three times with ethyl acetate, and then dry in a vacuum oven at 65℃ for 24h to obtain target product III.

[0135] The ratio of intermediate product II, glycidyl methacrylate, N,N-dimethylformamide C, and ethyl acetate is 10.208 g : 0.45 mmol : 200 mL : 400 mL.

[0136] The amount of hydroquinone used is 0.05 wt% of the amount of glycidyl methacrylate used;

[0137] Its infrared data is as follows: 3300-3500cm -1 -OH and -NH- are present; 1091 cm⁻¹ -1 -Si-O-Si- exists; 911cm -1 Epoxy groups are absent; 1654cm -1 -C=N- Exists; 1720cm -1 -C=O exists; 1611cm -1 811cm -1 -C = C - exists.

[0138] Example 7

[0139] An antibacterial dental restorative material, comprising the following raw materials in parts by weight:

[0140] 80 parts of modified filler;

[0141] 8 parts of bisphenol A-glycidyl methacrylate;

[0142] Two parts of glycidyl dimethacrylate;

[0143] 9 parts of triethylene dimethacrylate;

[0144] 1 part of photoinitiator (camphorquinone and ethyl 4-ethane-N,N-dimethylaminobenzoate in a mass ratio of 1:3.6).

[0145] The modified filler described above was prepared by the following method:

[0146] (1) Place silica (micron-sized silica and nano-sized silica in a mass ratio of 3.7:1) in a round-bottom flask, add KH560 and cyclohexane A successively, stir magnetically for 30 min at room temperature, and then heat and stir in an oil bath at 65℃ for 3 h; after the reaction is completed, filter, wash the insoluble matter three times with cyclohexane B and anhydrous ethanol, and then dry in a vacuum oven at 65℃ for 24 h to obtain intermediate product I;

[0147] The ratio of silica, KH560, cyclohexane A, cyclohexane B, and anhydrous ethanol is 10g:0.1g:100mL:300mL:400mL;

[0148] Its infrared data is as follows: 3433cm -1 -OH is present; 1091 cm⁻¹ -1 -Si-O-Si- exists; 911cm -1 Epoxy groups are present.

[0149] (2) Place intermediate product I and N,N-dimethylformamide A in a round-bottom flask, stir, and use a peristaltic pump to dropwise add to a three-necked flask containing 1,5-diguanidinylpentane and N,N-dimethylformamide B. Heat to 40°C and react for 4 hours. Filter, rinse the insoluble matter three times with deionized water, and then dry in a vacuum oven at 65°C for 24 hours to obtain intermediate product II.

[0150] The ratio of intermediate product I, N,N-dimethylformamide A, 1,5-diguanidinylpentane, N,N-dimethylformamide B, and deionized water is 10.10 g : 100 mL : 0.45 mmol : 150 mL : 400 mL;

[0151] Its infrared data is as follows: 3300-3500cm -1 -OH and -NH- are present; 1091 cm⁻¹ -1 -Si-O-Si- exists; 911cm -1 Epoxy groups disappear; 1654cm -1 :-C=N-exists.

[0152] (3) Add intermediate product II, glycidyl methacrylate, hydroquinone, and N,N-dimethylformyl C to a three-necked flask, stir, heat to 50℃ and react for 5h, then distill under reduced pressure, filter, wash the insoluble matter three times with ethyl acetate, and then dry in a vacuum oven at 65℃ for 24h to obtain target product III.

[0153] The ratio of intermediate product II, glycidyl methacrylate, N,N-dimethylformamide C, and ethyl acetate is 10.179 g : 0.45 mmol : 200 mL : 400 mL.

[0154] The amount of hydroquinone used is 0.05 wt% of the amount of glycidyl methacrylate used;

[0155] Its infrared data is as follows: 3300-3500cm -1 -OH and -NH- are present; 1091 cm⁻¹ -1 -Si-O-Si- exists; 911cm -1 Epoxy groups are absent; 1654cm -1 -C=N- Exists; 1720cm -1 -C=O exists; 1611cm -1 811cm -1 -C = C - exists.

[0156] The preparation method of the antibacterial dental restorative material described in Examples 1-7 includes the following steps:

[0157] In the dark, the modified filler and matrix resin are mixed in proportion, a photoinitiator is added, and after stirring evenly, the material is discharged to obtain the antibacterial dental restoration material.

[0158] Comparative Examples 1-7 are all compared with Example 1:

[0159] Comparative Example 1

[0160] An antibacterial dental restorative material, comprising the following raw materials in parts by weight:

[0161] 70 parts of modified filler;

[0162] 14 parts of bisphenol A-glycidyl methacrylate;

[0163] Two parts of glycidyl dimethacrylate;

[0164] 13 parts of triethylene dimethacrylate;

[0165] 1 part of photoinitiator (camphorquinone and ethyl 4-ethane-N,N-dimethylaminobenzoate in a mass ratio of 1:3.6).

[0166] The preparation method of the modified filler is the same as that in Specific Example 1, except that the mixture of micron-sized silica and nano-sized silica is replaced with pure micron-sized silica.

[0167] Comparative Example 2

[0168] An antibacterial dental restorative material, comprising the following raw materials in parts by weight:

[0169] 70 parts of modified filler;

[0170] 14 parts of bisphenol A-glycidyl methacrylate;

[0171] Two parts of glycidyl dimethacrylate;

[0172] 13 parts of triethylene dimethacrylate;

[0173] 1 part of photoinitiator (camphorquinone and ethyl 4-ethane-N,N-dimethylaminobenzoate in a mass ratio of 1:3.6).

[0174] The preparation method of the modified filler is the same as that in Specific Example 1, except that the mixture of micron-sized silica and nano-sized silica is replaced with pure nano-sized silica.

[0175] Implement Comparative Example 3

[0176] An antibacterial dental restorative material, comprising the following raw materials in parts by weight:

[0177] 70 parts of silica (micron-sized silica and nano-sized silica in a mass ratio of 3.7:1);

[0178] 14 parts of bisphenol A-glycidyl methacrylate;

[0179] Two parts of glycidyl dimethacrylate;

[0180] 13 parts of triethylene dimethacrylate;

[0181] 1 part of photoinitiator (camphorquinone and ethyl 4-ethane-N,N-dimethylaminobenzoate in a mass ratio of 1:3.6).

[0182] Comparative Example 4

[0183] An antibacterial dental restorative material, comprising the following raw materials in parts by weight:

[0184] 70 parts of modified filler;

[0185] 14 parts of bisphenol A-glycidyl methacrylate;

[0186] Two parts of glycidyl dimethacrylate;

[0187] 13 parts of triethylene dimethacrylate;

[0188] 1 part of photoinitiator (camphorquinone and ethyl 4-ethane-N,N-dimethylaminobenzoate in a mass ratio of 1:3.6).

[0189] The modified filler described above was prepared by the following method:

[0190] Protected from light, silica (micron-sized silica and nano-sized silica in a mass ratio of 3.7:1) 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 65 °C for 3 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 intermediate product I.

[0191] The ratio of silica, KH570, cyclohexane A, cyclohexane B, and anhydrous ethanol is 10g:0.1g:100mL:300mL:400mL;

[0192] Its infrared data is as follows: 3433cm -1 -OH is present; 1091 cm⁻¹ -1 -Si-O-Si- exists; 1721cm -1 -C=O exists; 1611cm -1 811cm -1 -C = C - exists.

[0193] Comparative Example 5

[0194] An antibacterial dental restorative material, comprising the following raw materials in parts by weight:

[0195] 69.4 parts of modified filler;

[0196] 0.6 parts of 1,10-diguanidinyldecane;

[0197] 14 parts of bisphenol A-glycidyl methacrylate;

[0198] Two parts of glycidyl dimethacrylate;

[0199] 13 parts of triethylene dimethacrylate;

[0200] 1 part of photoinitiator (camphorquinone and ethyl 4-ethane-N,N-dimethylaminobenzoate in a mass ratio of 1:3.6).

[0201] The preparation method of the modified filler is the same as that of Comparative Example 4.

[0202] Comparative Example 6

[0203] An antibacterial dental restorative material, comprising the following raw materials in parts by weight:

[0204] 69.4 parts of modified filler;

[0205] 0.6 parts of polyhexamethylene guanidine (average molecular weight 15000);

[0206] 14 parts of bisphenol A-glycidyl methacrylate;

[0207] Two parts of glycidyl dimethacrylate;

[0208] 13 parts of triethylene dimethacrylate;

[0209] 1 part of photoinitiator (camphorquinone and ethyl 4-ethane-N,N-dimethylaminobenzoate in a mass ratio of 1:3.6).

[0210] The preparation method of the modified filler is the same as that of Comparative Example 4.

[0211] Comparative Example 7

[0212] An antibacterial dental restorative material, comprising the following raw materials in parts by weight:

[0213] 70 parts of modified filler;

[0214] 14 parts of bisphenol A-glycidyl methacrylate;

[0215] Two parts of glycidyl dimethacrylate;

[0216] 13 parts of triethylene dimethacrylate;

[0217] 1 part of photoinitiator (camphorquinone and ethyl 4-ethane-N,N-dimethylaminobenzoate in a mass ratio of 1:3.6).

[0218] The modified filler described above was prepared by the following method:

[0219] (1) Place silica (micron-sized silica and nano-sized silica in a mass ratio of 3.7:1) in a round-bottom flask, add KH560 and cyclohexane A successively, stir magnetically for 30 min at room temperature, and then heat and stir in an oil bath at 65℃ for 3 h; after the reaction is completed, filter, wash the insoluble matter three times with cyclohexane B and anhydrous ethanol, and then dry in a vacuum oven at 65℃ for 24 h to obtain intermediate product I;

[0220] The ratio of silica, KH560, cyclohexane A, cyclohexane B, and anhydrous ethanol is 10g:0.1g:100mL:300mL:400mL;

[0221] Its infrared data is as follows: 3433cm -1 -OH is present; 1091 cm⁻¹ -1 -Si-O-Si- exists; 911cm -1 Epoxy groups are present.

[0222] (2) Place intermediate product I and N,N-dimethylformamide A in a round-bottom flask, stir, and use a peristaltic pump to dropwise add to a three-necked flask containing 1,10-diguanidinyldecane and N,N-dimethylformamide B. Heat to 40℃ and react for 4 hours. Filter, rinse the insoluble matter three times with deionized water, and then dry in a vacuum oven at 65℃ for 24 hours to obtain target product II.

[0223] The ratio of intermediate product I, N,N-dimethylformamide A, 1,10-diguanidinyldecane, N,N-dimethylformamide B, and deionized water is 10.10 g : 100 mL : 0.45 mmol : 150 mL : 400 mL;

[0224] Its infrared data is as follows: 3300-3500cm -1 -OH and -NH- are present; 1091 cm⁻¹ -1 -Si-O-Si- exists; 911cm -1 Epoxy groups disappear; 1654cm -1 :-C=N-exists.

[0225] The preparation method of the antibacterial dental restorative material described in Comparative Examples 1-7 is the same as that in Specific Example 1.

[0226] Using the antibacterial dental restorative materials obtained in Specific Examples 1-7 and Comparative Examples 1-7 as base materials, they were placed in a silicone rubber mold and cured for 10-200 seconds using a lamp with a wavelength of 410-500nm. 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.

[0227] The physical properties of the antibacterial dental restorative materials 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.

[0228] Table 1 Physical test performance of each embodiment

[0229]

[0230]

[0231] First, as can be seen from Table 1, the antibacterial dental restorative material of the present invention exhibits excellent mechanical properties, low shrinkage, antibacterial activity, and durable antibacterial properties, 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. It can be observed that chemical modification of the filler effectively wets and disperses nanomaterials, improving mechanical properties and reducing polymerization shrinkage. Examples 1 and Comparative Examples 4-7 demonstrate that the composite material of the present invention possesses excellent antibacterial activity and durable antibacterial properties; it also has a large molecular weight and long molecular chain, resulting in lower polymerization volume shrinkage and reduced internal stress, thus exhibiting superior mechanical properties.

[0232] The testing method is as follows:

[0233] (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.

[0234] (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.

[0235] Volumetric wear = (m2-m1) / ρ.

[0236] (3) 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.

[0237] (4) 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℃ constant temperature water bath shaking box. The test was carried out again on the 15th day.

[0238] 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. An antibacterial dental restorative material, characterized in that: The ingredients include the following parts by weight: 60-80 parts of modified filler; 19-39 parts of matrix resin; Photoinitiator 0.5-2 parts; The modified filler is prepared by the following method: (1) Place silica in a round-bottom flask, add KH560 and cyclohexane A one after another, stir magnetically for 30 min at room temperature, and then heat and stir in an oil bath at 60-70℃ for 2-4 h; after the reaction is completed, filter, wash the insoluble matter three times with cyclohexane B and anhydrous ethanol, and then dry in a vacuum oven at 65℃ for 24 h to obtain intermediate product I; The ratio of silica, KH560, cyclohexane A, cyclohexane B, and anhydrous ethanol is 10g:0.1g:100mL:300mL:400mL; (2) Place intermediate product I and N,N-dimethylformamide A in a round-bottom flask, stir, and add dropwise to a three-necked flask containing biguanide derivative and N,N-dimethylformamide B using a peristaltic pump. Heat to 30-50℃ and react for 3-6 hours. Filter, rinse the insoluble matter three times with deionized water, and then dry in a vacuum oven at 65℃ for 24 hours to obtain intermediate product II. The ratio of intermediate product I, N,N-dimethylformamide A, biguanide derivative, N,N-dimethylformamide B, and deionized water is as follows: 10.10g: 100mL: 0.45mmol: 150mL: 400mL; (3) Add intermediate product II, glycidyl methacrylate, hydroquinone, and N,N-dimethylformyl C to a three-necked flask, stir, heat to 40-60℃ and react for 3-6 hours, then distill under reduced pressure, filter, wash the insoluble matter three times with ethyl acetate, and then dry in a vacuum oven at 65℃ for 24 hours to obtain target product III. The ratio of intermediate product II, glycidyl methacrylate, N,N-dimethylformamide C, and ethyl acetate is as follows: 10.179-10.208g: 0.45mmol: 200mL: 400mL; The amount of hydroquinone used is 0.05 wt% of the amount of glycidyl methacrylate used; The silica is a mixture of micron-sized silica and nano-sized silica; The biguanide derivative is 1,5-diguanylpentane or 1,10-diguanyldecane; The matrix resin includes at least one of bisphenol A-glycidyl methacrylate, urethane dimethacrylate, and triethylene glycol dimethacrylate. The photoinitiator includes at least one of camphorquinone and ethyl 4-ethane-N,N-dimethylaminobenzoate.

2. The antibacterial dental restorative material 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 antibacterial dental restorative material according to claim 1, characterized in that: The photoinitiator is a mixture of camphorquinone and ethyl 4-ethane-N,N-dimethylaminobenzoate in a mass ratio of 1:2-4.

4. A method for preparing an antibacterial dental restorative material according to any one of claims 1-3, characterized in that: Includes the following steps: In the dark, the modified filler and matrix resin are mixed in proportion, a photoinitiator is added, and after stirring evenly, the material is discharged to obtain the antibacterial dental restoration material.

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