High-pollution-resistance light-cured resin for dental restoration and preparation method of high-pollution-resistance light-cured resin

Abstract

The invention discloses high-stain-resistance light-cured resin for dental restoration and a preparation method of the high-stain-resistance light-cured resin, and the high-stain-resistance light-cured resin comprises the following raw material components in parts by weight: 60-90 parts of vinyl-containing polysiloxane; 5-35 parts of a hydrophilic monomer; 0.05 to 15 parts of a photosensitizer; 0-10 parts of a diluent; and 0-30 parts of a reinforcing agent. The preparation method comprises the following steps: S1, preparing a hydrophobic reaction solution and a hydrophilic reaction solution; s2, uniformly mixing the two to obtain a mixture; s3, the mixture is subjected to light curing, and the high-pollution-resistance light-cured resin for dental restoration is obtained. The high-pollution-resistance light-cured resin for dental restoration prepared by the invention has good pollution resistance, and is simple in process, relatively low in cost, free of use of a solvent and high in curing speed; and the problems that hydrophilic monomers such as vinyl pyrrolidine anti-fouling components are dissolved and peeled off when encountering water can be effectively avoided.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials and light-curing for dental restoration, and in particular relates to a highly anti-fouling light-curing resin for dental restoration and a preparation method thereof. Background Art

[0002] With the continuous improvement of material synthesis and modification technology and processing and molding methods, composite resin materials have become the main materials to replace traditional silver-mercury alloy restoration materials due to their excellent aesthetic properties, simple and fast clinical operation, good adhesion to the tooth body and low safety risks. They have been rapidly developed and more and more widely used in the field of dental restoration. However, the current commercial composite resin materials for dental restoration basically do not have anti-fouling properties, resulting in a large number of oral bacteria, intercellular substances, white blood cells, desquamated epithelial cells and food debris adhering to and accumulating on teeth and other oral soft tissues to form microbial film groups and produce dental plaque, causing oral infections such as gingivitis and periodontitis, and may even cause the occurrence of secondary caries and damage the dental pulp, increasing the risk of various oral diseases. Most of the current anti-fouling performance research focuses on increasing the antibacterial efficacy of composite resins by adding antibacterial monomers or antibacterial fillers, which is passive contact antibacterial and bactericidal, and few studies focus on the active anti-fouling properties of dental restoration materials in many aspects. Therefore, it is necessary to develop composite resin materials with high anti-fouling effects, so that the materials have excellent anti-bacterial, anti-cell and food debris adhesion properties, inhibit protein adsorption and other anti-fouling effects, thereby effectively reducing the accumulation of plaque on the surface of tooth tissue and dental materials, which is of great clinical significance for preventing various oral diseases.

[0003] In addition, hydrophilic monomers such as vinyl pyrrolidone compounds have good water solubility and physiological inertness, and do not cause any irritation to human tissues. The pyrrolidone unit can tightly bind to water molecules and form a hydration layer on the surface of the material. At the same time, because it is electrically neutral, it can effectively eliminate the electrostatic force and hydrophobic force between biological macromolecules such as bacteria, cells, and proteins and the surface of the material, and then form a barrier interface with excellent anti-fouling performance on the surface of the material. Therefore, vinyl pyrrolidone compounds are often used in the preparation of anti-fouling coatings on the surfaces of various biomedical materials and devices. However, due to the problems of easy peeling of the anti-fouling coating on the surface of the material and the loss of dissolution in water, the long-term anti-fouling effect in practical applications is not ideal, so it is necessary to seek to prepare a material that can be durable and highly effective in anti-fouling. Summary of the invention

[0004] The present invention aims to solve the problem that the current dental restoration materials have insufficient anti-fouling performance, and provides a highly anti-fouling photocurable resin for dental restoration and a preparation method thereof. The photocurable resin for dental restoration of the present invention has good anti-fouling performance, simple process, low cost, no need to use solvents, fast curing speed, and can effectively avoid the problem of hydrophilic monomers such as vinyl pyrrolidone anti-fouling components dissolving and peeling when in contact with water.

[0005] In order to achieve the purpose of the present invention, the present invention adopts the following technical solutions:

[0006] In a first aspect, the present invention provides a highly stain-resistant photocurable resin for dental restoration, comprising the following raw material components by weight:

[0007] 60-90 parts of vinyl-containing polysiloxane;

[0008] 5-35 parts of hydrophilic monomer;

[0009] Photosensitizer 0.05-15 parts;

[0010] Diluent 0-10 parts;

[0011] Enhancer 0-30 parts;

[0012] The hydrophilic monomer includes one or more of N-vinylpyrrolidone, N-vinylpiperidone, N-vinyl-ε-caprolactam, N-vinyl-N-methylacetamide, N-vinylimidazolidinone, N-vinylsuccinimide, N-vinylacetamide, and 3-Boc-5-vinyl-2-oxazolidinone.

[0013] In some embodiments of the present invention, the vinyl-containing polysiloxane includes one or more of vinyl-terminated dimethyl polysiloxane, vinyl-terminated methyl vinyl polysiloxane, divinyl-terminated poly (dimethylsiloxane-co-diphenylsiloxane), vinyl-terminated methyl phenyl polysiloxane, vinyl-terminated dimethyl methyl vinyl (siloxane and polysiloxane), vinyl-terminated methyl phenyl polysiloxane, and α, ω-divinyl polymethyl trifluoropropyl siloxane.

[0014] In some embodiments of the present invention, the viscosity of the vinyl-containing polysiloxane is in the range of 50-80000 cp, and its molecular structure is linear or three-dimensional network.

[0015] In some embodiments of the present invention, the photosensitizer includes one or more of Irgacure 2959, Irgacure 184, Irgacure 907, Irgacure 819, BPO, XBPO, TPO, TPO-L, TMO, Darocure 1173, camphorquinone, furil, and 1-phenyl-1,2-propanedione.

[0016] In some embodiments of the present invention, the diluent includes one or more of acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, n-butyl methacrylate, benzyl acrylic acid, hydroxypropyl methacrylate, furfuryl methacrylate, cyclohexyl methacrylate, ethyl 2-phenylacrylate, diethylene glycol diacrylate, and 9-anthracenemethyl acrylate.

[0017] In some embodiments of the present invention, the reinforcing agent includes one or more of silicon dioxide, kaolin, and hydroxyapatite.

[0018] In some embodiments of the present invention, the radiation intensity of the photocuring is 50-120 mW / cm 2 The irradiation time of photocuring is 5s-40min, and the wavelength range of photocuring is 100-400nm.

[0019] In some embodiments of the present invention, the water contact angle of the photocurable resin is 30-90°, preferably 30-80°, and more preferably 30-75°.

[0020] In a second aspect, the present invention provides a method for preparing the highly anti-fouling photocurable resin for dental restoration as described above, comprising the following steps:

[0021] S1. Preparation of hydrophobic reaction solution and hydrophilic reaction solution:

[0022] The vinyl-containing polysiloxane, a part of the photosensitizer and an optional enhancer are uniformly mixed to obtain a hydrophobic reaction solution for standby use; the hydrophilic monomer, the remaining photosensitizer and an optional diluent are uniformly mixed to obtain a hydrophilic reaction solution for standby use;

[0023] S2, mixing the hydrophobic reaction solution and the hydrophilic reaction solution uniformly to obtain a mixture;

[0024] S3, placing the mixture of step S2 into a molding mold for light curing to obtain a highly stain-resistant light-curable resin for dental restoration.

[0025] In the method for preparing the highly anti-fouling photocurable resin for dental restoration of the present invention, the irradiation intensity of the photocuring is 50-120 mW / cm 2The irradiation time of photocuring is 5s-40min, and the wavelength range of photocuring is 100-400nm.

[0026] In a third aspect, the present invention provides a highly stain-resistant photocurable resin for dental restoration as described above or a highly stain-resistant photocurable resin prepared by the method for preparing the highly stain-resistant photocurable resin for dental restoration as described above, and its use in dental restoration, preferably,

[0027] The application of the dental restoration includes application in dental restoration and denture restoration.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] 1. The photocurable resin for dental restoration of the present invention is prepared by introducing a hydrophilic monomer having antifouling effect into a polysiloxane photocurable resin system containing a vinyl group, and forming a photocurable resin material having a three-dimensional stable covalent cross-linked structure through an ultraviolet light curing reaction.

[0030] 2. The photocurable resin for dental restoration provided by the present invention not only has the excellent mechanical durability and biological inertness of silane copolymers, but also permanently fixes the water-soluble hydrophilic monomer anti-fouling components in the resin, thereby greatly improving its anti-fouling stability and durability in water. It has a good preventive effect on the occurrence of oral diseases such as dental plaque and periodontitis, and has very good clinical application prospects. Description of the drawings:

[0031] Figure 1 is the contact angle of the surface of the pure polysiloxane sample without hydrophilic monomer in Comparative Example 1;

[0032] Figure 2 is the contact angle of the surface of the highly anti-fouling photocurable resin sample for dental restoration of Example 1;

[0033] Figure 3 This is the result of the cell adhesion test on the surface of the pure polysiloxane sample without hydrophilic monomer in Comparative Example 1;

[0034] Figure 4 These are the results of the cell adhesion experiment on the surface of the highly anti-fouling photocurable resin sample for dental restoration in Example 1. DETAILED DESCRIPTION

[0035] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention. Some non-essential improvements and adjustments made by technicians in this field based on the content of the present invention should be regarded as the protection scope of the present invention.

[0036] The inventors have discovered through research that a photocurable resin material having a three-dimensional stable covalent cross-linked structure can be formed by using a polysiloxane containing a vinyl group and a hydrophilic monomer having anti-fouling properties through an ultraviolet light curing reaction. The anti-fouling components of the hydrophilic monomer can be firmly fixed by the polysiloxane polymer in the form of chemical covalent bonds, effectively avoiding the dissolution of the anti-fouling components in the system when encountering water, thereby improving the durable anti-fouling properties of the material.

[0037] Based on the above viewpoints, in a first aspect, the present invention provides a highly stain-resistant photocurable resin for dental restoration, comprising the following raw material components by weight:

[0038] 60wt%-90wt% of vinyl-containing polysiloxane;

[0039] 5-35 parts of hydrophilic monomer;

[0040] Photosensitizer 0.05-15 parts;

[0041] Diluent 0-10 parts;

[0042] Enhancer 0-30 parts;

[0043] The hydrophilic monomer includes one or more of N-vinylpyrrolidone, N-vinylpiperidone, N-vinyl-ε-caprolactam, N-vinyl-N-methylacetamide, N-vinylimidazolidinone, N-vinylsuccinimide, N-vinylacetamide, and 3-Boc-5-vinyl-2-oxazolidinone.

[0044] In some embodiments of the present invention, the vinyl-containing polysiloxane includes polysiloxanes containing terminal vinyl or side chain vinyl commonly used in the art, and specifically may include one or more of terminal vinyl-terminated dimethyl polysiloxane, vinyl-terminated methyl vinyl polysiloxane, divinyl-terminated poly (dimethylsiloxane-co-diphenylsiloxane), vinyl-terminated methyl phenyl polysiloxane, vinyl-terminated dimethyl methyl vinyl (siloxane and polysiloxane), vinyl-terminated methyl phenyl polysiloxane, and α,ω-divinyl polymethyl trifluoropropyl siloxane.

[0045] In some embodiments of the present invention, the viscosity of the vinyl-containing polysiloxane is in the range of 50-80000 cp, and its molecular structure is linear or three-dimensional network.

[0046] In some embodiments of the present invention, the photosensitizer includes one or more of Irgacure 2959, Irgacure 184, Irgacure 907, Irgacure 819, BPO, XBPO, TPO, TPO-L, TMO, Darocure 1173, camphorquinone, furil, and 1-phenyl-1,2-propanedione.

[0047] In some embodiments of the present invention, the diluent includes one or more of acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, n-butyl methacrylate, benzyl acrylic acid, hydroxypropyl methacrylate, furfuryl methacrylate, cyclohexyl methacrylate, ethyl 2-phenylacrylate, diethylene glycol diacrylate, and 9-anthracenemethyl acrylate.

[0048] In some embodiments of the present invention, the reinforcing agent is a filler commonly used in the art, including one or more of silicon dioxide, kaolin, and hydroxyapatite.

[0049] In some embodiments of the present invention, the radiation intensity of the photocuring is 50-120 mW / cm 2 The irradiation time of photocuring is 5s-40min, and the wavelength range of photocuring is 100-400nm.

[0050] In some embodiments of the present invention, the water contact angle of the photocurable resin is 30-90°, preferably 30-80°, and more preferably 30-75°.

[0051] In a second aspect, the present invention provides a method for preparing the highly anti-fouling photocurable resin for dental restoration as described above, comprising the following steps:

[0052] S1. Preparation of hydrophobic reaction solution and hydrophilic reaction solution:

[0053] The vinyl-containing polysiloxane, a part of the photosensitizer and an optional enhancer are uniformly mixed to obtain a hydrophobic reaction solution for standby use; the hydrophilic monomer, the remaining photosensitizer and an optional diluent are uniformly mixed to obtain a hydrophilic reaction solution for standby use;

[0054] S2, mixing the hydrophobic reaction solution and the hydrophilic reaction solution uniformly to obtain a mixture;

[0055] S3, placing the mixture of step 2 into a molding mold for light curing to obtain a highly stain-resistant light-curable resin for dental restoration.

[0056] In the method for preparing the highly anti-fouling photocurable resin for dental restoration of the present invention, the irradiation intensity of the photocuring is 50-120 mW / cm 2The irradiation time of photocuring is 5s-40min, and the wavelength range of photocuring is 100-400nm.

[0057] In a third aspect, the present invention also provides a highly stain-resistant photocurable resin for dental restoration as described above or a highly stain-resistant photocurable resin prepared by the preparation method of the highly stain-resistant photocurable resin for dental restoration as described above in dental restoration. Preferably, the application of dental restoration includes application in dental restoration and denture restoration.

[0058] The highly stain-resistant light-curable resin for dental restoration of the present invention is tested by the following method:

[0059] Water contact angle: The static water droplet contact angle of the sample surface was tested using a 5 μL water droplet on a contact angle meter.

[0060] Cell adhesion experiment: L929 cells were cultured in DMEM supplemented with 10.0% FBS and 1.0% penicillin-streptomycin in a 5.0% CO2 balanced air incubator at 37°C. The cells were passaged by 0.25% trypsin digestion at 37°C. The highly antifouling photocurable resin circular sample with high antifouling efficacy prepared by the method of the present invention and the pure polysiloxane circular sample without hydrophilic monomer were sterilized and placed in a 24-well plate, and the cells were inoculated at a concentration of 2×104 cells. After 1 day, the material was taken out, fixed and washed, and then stained with FITC for 20 minutes. The cell morphology on the material was observed using a fluorescence microscope.

[0061] The beneficial effects of the present invention will be further described below in conjunction with the embodiments and comparative examples. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0062] The manufacturers and brands of the raw materials used in Examples 1-4 of the present invention and Comparative Example 1 are shown in Table 1.

[0063] Table 1 shows the manufacturers and brands of the raw materials used in the examples:

[0064]

[0065]

[0066] Example 1

[0067] A highly stain-resistant light-curable resin for dental restoration, which is made of the following raw material components in parts by weight:

[0068] Hydrophobic reaction solution:

[0069] 60 parts of vinyl-terminated dimethyl polysiloxane;

[0070] 10 parts of silicon dioxide;

[0071] Irgacure 2959 1 copy;

[0072] Hydrophilic reaction solution:

[0073] 20 parts of N-vinyl pyrrolidone;

[0074] Acrylic acid 8 parts;

[0075] Irgacure 2959 1 serving.

[0076] The method for preparing the above-mentioned highly anti-fouling photocurable resin for dental restoration comprises the following steps:

[0077] S1. Preparation of hydrophobic reaction liquid and hydrophilic reaction liquid: 60 parts of vinyl-terminated dimethyl polysiloxane, 1 part of Irgacure 2959 and 10 parts of silicon dioxide are mixed evenly to obtain a hydrophobic reaction liquid, which is set aside; 20 parts of N-vinyl pyrrolidone, 1 part of Irgacure 2959 and 8 parts of acrylic acid are mixed evenly to obtain a hydrophilic reaction liquid, which is set aside;

[0078] S2, mixing the hydrophobic reaction solution and the hydrophilic reaction solution uniformly to obtain a mixture;

[0079] S3, placing the mixture of step S2 into a molding mold for light curing to obtain a highly stain-resistant light-curable resin for dental restoration.

[0080] The light curing conditions are as follows: the irradiation intensity is 70mW / cm 2 , vacuum section (wavelength 100-200nm) curing for 10min, short wave section (wavelength 200-280nm) for 10min, medium wave section (wavelength 280-315nm) for 10min, long wave section (wavelength 315-400nm) for 10min.

[0081] Example 2

[0082] A highly stain-resistant light-curable resin for dental restoration, which is made of the following raw material components in parts by weight:

[0083] Hydrophobic reaction solution:

[0084] Divinyl-terminated poly(dimethylsiloxane-co-diphenylsiloxane) 70 parts;

[0085] 5 parts of silicon dioxide;

[0086] Irgacure 907 7 copies;

[0087] Hydrophilic reaction solution:

[0088] 10 parts of N-vinyl-ε-caprolactam;

[0089] 5 parts of methyl acrylate;

[0090] Irgacure 907 3 servings.

[0091] The method for preparing the above-mentioned highly anti-fouling photocurable resin for dental restoration comprises the following steps:

[0092] S1. Preparation of hydrophobic reaction liquid and hydrophilic reaction liquid: 70 parts of divinyl-terminated poly(dimethylsiloxane-co-diphenylsiloxane), 7 parts of Irgacure 907 and 5 parts of silicon dioxide are mixed evenly to obtain a hydrophobic reaction liquid, which is set aside; 10 parts of N-vinyl-ε-caprolactam, 3 parts of Irgacure 907 and 5 parts of methyl acrylate are mixed evenly to obtain a hydrophilic reaction liquid, which is set aside;

[0093] S2, mixing the hydrophobic reaction solution and the hydrophilic reaction solution uniformly to obtain a mixture;

[0094] S3, placing the mixture of step S2 into a molding mold for light curing to obtain a highly stain-resistant light-curable resin for dental restoration.

[0095] The light curing conditions are as follows: irradiation intensity is 120mW / cm 2 , vacuum section (wavelength 100-200nm) curing for 1s, short wave band (wavelength 200-280nm) for 1s, medium wave band (wavelength 280-315nm) for 1s, long wave band (wavelength 315-400nm) for 2s.

[0096] Example 3

[0097] A highly stain-resistant light-curable resin for dental restoration, which is made of the following raw material components in parts by weight:

[0098] Hydrophobic reaction solution:

[0099] Vinyl terminated dimethyl methyl vinyl (siloxane and polysiloxane) 78 parts;

[0100] 5 parts of kaolin;

[0101] TPO 5 copies;

[0102] Hydrophilic reaction solution:

[0103] 5 parts of N-vinyl-N-methylacetamide;

[0104] 5 parts of n-butyl acrylate;

[0105] TPO 2 parts.

[0106] The method for preparing the above-mentioned highly anti-fouling photocurable resin for dental restoration comprises the following steps:

[0107] S1. Preparation of hydrophobic reaction liquid and hydrophilic reaction liquid: 78 parts of vinyl-terminated dimethyl methyl vinyl (siloxane and polysiloxane), 5 parts of TPO and 5 parts of kaolin are mixed evenly to obtain a hydrophobic reaction liquid, which is set aside; 5 parts of N-vinyl-N-methylacetamide, 2 parts of TPO and 5 parts of n-butyl acrylate are mixed evenly to obtain a hydrophilic reaction liquid, which is set aside;

[0108] S2, mixing the hydrophobic reaction solution and the hydrophilic reaction solution uniformly to obtain a mixture;

[0109] S3, placing the mixture of step S2 into a molding mold for light curing to obtain a highly stain-resistant light-curable resin for dental restoration.

[0110] The light curing conditions are as follows: the irradiation intensity is 100mW / cm 2 , vacuum section (wavelength 100-200nm) curing for 1min, short wave section (wavelength 200-280nm) for 1min, medium wave section (wavelength 280-315nm) for 1min, long wave section (wavelength 315-400nm) for 1min.

[0111] Example 4

[0112] A highly stain-resistant light-curable resin for dental restoration, which is made of the following raw material components in parts by weight:

[0113] Hydrophobic reaction solution:

[0114] 87 parts of vinyl-terminated methylphenyl polysiloxane;

[0115] 3 parts of kaolin;

[0116] 2 parts of camphorquinone;

[0117] Hydrophilic reaction solution:

[0118] 5 parts of N-vinyl acetamide;

[0119] 1 part of diethylene glycol diacrylate;

[0120] 2 parts of camphorquinone.

[0121] The method for preparing the above-mentioned highly anti-fouling photocurable resin for dental restoration comprises the following steps:

[0122] S1. Preparation of a hydrophobic reaction solution and a hydrophilic reaction solution: 87 parts of vinyl-terminated methylphenyl polysiloxane, 2 parts of camphorquinone and 3 parts of kaolin are uniformly mixed to obtain a hydrophobic reaction solution for standby use; 5 parts of N-vinylacetamide, 2 parts of camphorquinone and 1 part of diethylene glycol diacrylate are uniformly mixed to obtain a hydrophilic reaction solution for standby use;

[0123] S2, mixing the hydrophobic reaction solution and the hydrophilic reaction solution uniformly to obtain a mixture;

[0124] S3, placing the mixture of step S2 into a molding mold for light curing to obtain a highly stain-resistant light-curable resin for dental restoration.

[0125] The light curing conditions are as follows: the irradiation intensity is 100mW / cm 2 , vacuum section (wavelength 100-200nm) curing for 1min, short wave band (wavelength 200-280nm) for 5min, medium wave band (wavelength 280-315nm) for 1min, long wave band (wavelength 315-400nm) for 5min.

[0126] Example 5

[0127] A highly stain-resistant light-curable resin for dental restoration, which is made of the following raw material components in parts by weight:

[0128] Hydrophobic reaction solution:

[0129] 60 parts of divinyl-terminated poly(dimethylsiloxane-co-diphenylsiloxane);

[0130] 1 part of hydroxyapatite;

[0131] 1 part of furil;

[0132] Hydrophilic reaction solution:

[0133] 3-Boc-5-vinyl-2-oxazolidinone 35 parts;

[0134] 2 parts of 9-anthracenemethyl acrylate;

[0135] 1 part of furil.

[0136] The method for preparing the above-mentioned highly anti-fouling photocurable resin for dental restoration comprises the following steps:

[0137] S1, preparation of hydrophobic reaction liquid and hydrophilic reaction liquid: 60 parts of divinyl-terminated poly(dimethylsiloxane-co-diphenylsiloxane), 1 part of furil and 1 part of hydroxyapatite are mixed evenly to obtain a hydrophobic reaction liquid, which is set aside; 35 parts of 3-Boc-5-vinyl-2-oxazolidinone, 1 part of furil and 2 parts of 9-anthracenemethyl acrylate are mixed evenly to obtain a hydrophilic reaction liquid, which is set aside;

[0138] S2, mixing the hydrophobic reaction solution and the hydrophilic reaction solution uniformly to obtain a mixture;

[0139] S3, placing the mixture of step S2 into a molding mold for light curing to obtain a highly stain-resistant light-curable resin for dental restoration.

[0140] The light curing conditions are as follows: the irradiation intensity is 70mW / cm 2 , vacuum section (wavelength 100-200nm) curing for 5min, short wave section (wavelength 200-280nm) for 5min, medium wave section (wavelength 280-315nm) for 5min, long wave section (wavelength 315-400nm) for 5min.

[0141] Example 6

[0142] A highly stain-resistant light-curable resin for dental restoration, which is made of the following raw material components in parts by weight:

[0143] Hydrophobic reaction solution:

[0144] 60 parts of vinyl-terminated methylphenyl polysiloxane;

[0145] Hydroxyapatite 30 parts;

[0146] 1 part of 1-phenyl-1,2-propanedione;

[0147] Hydrophilic reaction solution:

[0148] 3-Boc-5-vinyl-2-oxazolidinone 6 parts;

[0149] 2 parts of acrylic acid;

[0150] 1-phenyl-1,2-propanedione 1 part.

[0151] The method for preparing the above-mentioned highly anti-fouling photocurable resin for dental restoration comprises the following steps:

[0152] S1. Preparation of a hydrophobic reaction liquid and a hydrophilic reaction liquid: 60 parts of vinyl-terminated methylphenyl polysiloxane, 1 part of 1-phenyl-1,2-propanedione and 30 parts of hydroxyapatite are mixed evenly to obtain a hydrophobic reaction liquid for standby use; 6 parts of 3-Boc-5-vinyl-2-oxazolidinone, 1 part of 1-phenyl-1,2-propanedione and 2 parts of acrylic acid are mixed evenly to obtain a hydrophilic reaction liquid for standby use;

[0153] S2, mixing the hydrophobic reaction solution and the hydrophilic reaction solution uniformly to obtain a mixture;

[0154] S3, placing the mixture of step S2 into a molding mold for light curing to obtain a highly stain-resistant light-curable resin for dental restoration.

[0155] The light curing conditions are as follows: irradiation intensity is 50mW / cm 2 , vacuum section (wavelength 100-200nm) curing for 10min, short wave section (wavelength 200-280nm) for 5min, medium wave section (wavelength 280-315nm) for 5min, long wave section (wavelength 315-400nm) for 10min.

[0156] Comparative Example 1

[0157] A highly stain-resistant light-curable resin for dental restoration, which is made of the following raw material components in parts by weight:

[0158] Hydrophobic reaction solution:

[0159] 80 parts of vinyl-terminated dimethyl polysiloxane;

[0160] 10 parts of silicon dioxide;

[0161] Irgacure 2959 1 copy;

[0162] Hydrophilic reaction solution:

[0163] Acrylic acid 8 parts;

[0164] Irgacure 2959 1 serving.

[0165] The method for preparing the above-mentioned highly anti-fouling photocurable resin for dental restoration comprises the following steps:

[0166] S1. Preparation of hydrophobic reaction liquid and hydrophilic reaction liquid: 80 parts of vinyl-terminated dimethyl polysiloxane, 1 part of Irgacure 2959 and 10 parts of silicon dioxide are mixed evenly to obtain a hydrophobic reaction liquid, which is set aside; 1 part of Irgacure 2959 and 8 parts of acrylic acid are mixed evenly to obtain a hydrophilic reaction liquid, which is set aside;

[0167] S2, mixing the hydrophobic reaction solution and the hydrophilic reaction solution uniformly to obtain a mixture;

[0168] S3, placing the mixture of step S2 into a molding mold for light curing to obtain a highly stain-resistant light-curable resin for dental restoration.

[0169] The light curing conditions are as follows: the irradiation intensity is 70mW / cm 2 , vacuum section (wavelength 100-200nm) curing for 10min, short wave section (wavelength 200-280nm) for 10min, medium wave section (wavelength 280-315nm) for 10min, long wave section (wavelength 315-400nm) for 10min.

[0170] in, Figure 1 The surface of the sample of Comparative Example 1, which is pure polysiloxane without a hydrophilic monomer, is in a hydrophobic state. Figure 2 It shows that the surface of the sample of Example 1 after the antifouling modification of the present invention is in a hydrophilic state. Figure 3 The sample of Comparative Example 1, which is pure polysiloxane without a hydrophilic monomer, showed a large amount of cell adhesion on its surface. Figure 4 There is almost no obvious cell adhesion on the surface of the sample of Example 1 after the anti-fouling modification of the present invention. The results show that compared with the polysilane material without hydrophilic monomer modification, the anti-fouling performance of the highly anti-fouling photocurable resin for dental restoration prepared by the present invention is significantly improved.

Claims

1. A highly stain-resistant light-curable resin for dental restoration, comprising the following raw material components by weight: 60-90 parts of vinyl-containing polysiloxane; 5-35 parts of hydrophilic monomer; Photosensitizer 0.05-15 parts; Diluent 0-10 parts; Enhancer 0-30 parts; The hydrophilic monomer includes one or more of N-vinylpyrrolidone, N-vinylpiperidone, N-vinyl-ε-caprolactam, N-vinyl-N-methylacetamide, N-vinylimidazolidinone, N-vinylsuccinimide, N-vinylacetamide, and 3-Boc-5-vinyl-2-oxazolidinone.

2. The highly anti-fouling photocurable resin according to claim 1, characterized in that: The vinyl-containing polysiloxane includes one or more of vinyl-terminated dimethyl polysiloxane, vinyl-terminated methyl vinyl polysiloxane, divinyl-terminated poly (dimethylsiloxane-co-diphenylsiloxane), vinyl-terminated methyl phenyl polysiloxane, vinyl-terminated dimethyl methyl vinyl (siloxane and polysiloxane), vinyl-terminated methyl phenyl polysiloxane, and α,ω-divinyl polymethyl trifluoropropyl siloxane.

3. The highly anti-fouling photocurable resin according to claim 1, characterized in that: The viscosity of the vinyl-containing polysiloxane is in the range of 50-80000cp, and its molecular structure is linear or three-dimensional network.

4. The highly anti-fouling photocurable resin according to any one of claims 1 to 3, characterized in that: The photosensitizer includes one or more of Irgacure 2959, Irgacure 184, Irgacure 907, Irgacure 819, BPO, XBPO, TPO, TPO-L, TMO, Darocure 1173, camphorquinone, furil, and 1-phenyl-1,2-propanedione.

5. The highly anti-fouling photocurable resin according to any one of claims 1 to 3, characterized in that: The diluent includes one or more of acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, n-butyl methacrylate, benzyl acrylic acid, hydroxypropyl methacrylate, furfuryl methacrylate, cyclohexyl methacrylate, ethyl 2-phenylacrylate, diethylene glycol diacrylate, and 9-anthracenemethyl acrylate.

6. The highly anti-fouling photocurable resin according to any one of claims 1 to 3, characterized in that: The reinforcing agent includes one or more of silicon dioxide, kaolin and hydroxyapatite.

7. The highly anti-fouling photocurable resin according to any one of claims 1 to 3, characterized in that: The radiation intensity of light curing is 50-120mW / cm 2 The irradiation time of photocuring is 5s-40min, and the wavelength range of photocuring is 100-400nm.

8. The highly anti-fouling photocurable resin according to any one of claims 1 to 3, characterized in that: The water contact angle of the highly anti-fouling photocurable resin is 30-90°, preferably 30-80°, and more preferably 30-75°.

9. A method for preparing a highly stain-resistant photocurable resin for dental restoration according to any one of claims 1 to 8, comprising the following steps: S1. Preparation of hydrophobic reaction solution and hydrophilic reaction solution: The vinyl-containing polysiloxane, a part of the photosensitizer and an optional enhancer are uniformly mixed to obtain a hydrophobic reaction solution for standby use; the hydrophilic monomer, the remaining photosensitizer and an optional diluent are uniformly mixed to obtain a hydrophilic reaction solution for standby use; S2, mixing the hydrophobic reaction solution and the hydrophilic reaction solution uniformly to obtain a mixture; S3, placing the mixture of step S2 into a molding mold for light curing to obtain a highly stain-resistant light-curable resin for dental restoration.

10. Use of the highly stain-resistant photocurable resin for dental restoration as described in claims 1 to 8 or the highly stain-resistant photocurable resin for dental restoration prepared by the preparation method described in claim 9 in dental restoration, preferably, the application of dental restoration includes application in dental restoration and denture restoration.

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