High-stability wear-resistant bio-based hydrophobic resin composition, dental material, preparation method and application

Abstract

The invention provides a high-stability wear-resistant bio-based hydrophobic resin composition, a dental material, a preparation method and application, and relates to the technical field of biomedical materials. The invention provides a high-stability wear-resistant bio-based hydrophobic resin composition. The coating is prepared from epoxy soybean oil acrylate, triethylene glycol dimethacrylate, perfluoroalkyl acrylate, hydrophilic nano silicon dioxide, hydrophobic nano silicon dioxide, gamma-methacryloyloxypropyltrimethoxysilane, camphorquinone and ethyl 4-dimethylaminobenzoate. According to the invention, epoxy soybean oil acrylate is used as a resin matrix to replace common bisphenol A resin, so that the adhesive is more environment-friendly and has sustainability; and hydrophilic nano silicon dioxide and hydrophobic nano silicon dioxide are introduced, so that the hydrophobic stability of the material is improved while the mechanical property is enhanced, and the hydrophobic property is not easy to decline after cold and hot cycling treatment.

Description

Technical Field

[0001] The invention belongs to the technical field of biomedical materials, and in particular relates to a high-stability, wear-resistant bio-based hydrophobic resin composition, a dental material, and a preparation method and application thereof. Background Art

[0002] Caries is a disease in which the hard tissues of the teeth are destroyed chronically. Caries and its complications can aggravate or induce systemic diseases, seriously endangering human health, and have been listed as the third largest non-communicable disease by the World Health Organization. At present, resin-based materials containing bisphenol A diglycidyl methacrylate (Bis-GMA) are widely used in oral clinics. However, bisphenol A (BPA) and its derivatives have been identified as endocrine disruptors that can effectively bind to and activate estrogen receptors. They can be ingested and absorbed by the oral and gastrointestinal mucosa, leading to local and systemic toxicity. In addition, BPA is a non-renewable raw material from limited petroleum resources. Therefore, it is necessary to seek a new environmentally friendly bio-based resin to replace the bisphenol A type resin in the current oral resin-based composite materials for the research of oral resin materials. In addition, the existing oral materials have poor stability and the hydrophobic properties are easily reduced when exposed to heat or cold.

[0003] In view of this, it is necessary to design a green and environmentally friendly bio-based hydrophobic resin that has high hydrophobic stability while maintaining mechanical properties to extend the service life of dental materials. Summary of the invention

[0004] The purpose of the present invention is to provide a high-stability wear-resistant bio-based hydrophobic resin composition, a dental material, and a preparation method and application. The high-stability wear-resistant bio-based hydrophobic resin composition provided by the present invention uses bio-based resin as the main raw material, is environmentally friendly, and the prepared dental material improves the hydrophobic stability of the material while enhancing the mechanical properties, and the hydrophobic performance is not easily reduced after hot and cold cycle treatment.

[0005] The present invention provides the following technical solutions.

[0006] The invention provides a high-stability wear-resistant bio-based hydrophobic resin composition, which comprises the following components, measured by mass: 2-8 parts of epoxy soybean oil acrylate, 16-24 parts of triethylene glycol dimethacrylate, 5-15 parts of perfluoroalkyl acrylate, 2-15 parts of hydrophilic nano-silica, 2-15 parts of hydrophobic nano-silica, 5-15 parts of gamma-methacryloxypropyltrimethoxysilane, 0.02-0.2 parts of camphorquinone and 0.12-0.3 parts of ethyl 4-dimethylaminobenzoate.

[0007] Preferably, based on the total mass of the hydrophilic nano-silica and the hydrophobic nano-silica being 100%, the mass fraction of the hydrophobic nano-silica is 20-80%.

[0008] Preferably, the particle size of the hydrophilic nano-silica is 15 to 20 nm.

[0009] Preferably, the hydrophobic nano-silica is obtained by modifying hydrophilic nano-silica with 1H,1H,2H,2H-perfluorodecyltriethoxysilane.

[0010] Preferably, the mixture further comprises 2 to 10 parts of a diluent, wherein the diluent is an alcohol solvent.

[0011] The present invention also provides a method for preparing the above-mentioned high-stability wear-resistant bio-based hydrophobic resin composition, comprising the following steps:

[0012] Epoxidized soybean oil acrylate, triethylene glycol dimethacrylate, perfluoroalkyl acrylate, diluent, hydrophilic nano-silica, hydrophobic nano-silica, γ-methacryloxypropyltrimethoxysilane, camphorquinone and ethyl 4-dimethylaminobenzoate are mixed to obtain the high-stability wear-resistant bio-based hydrophobic resin composition.

[0013] Preferably, the mixing is carried out in a light-proof condition; the mixing time is 1.5 to 6.5 hours; the mixing method is magnetic stirring mixing, and the speed of the magnetic stirring mixing is 720 to 800 rpm / min.

[0014] The present invention also provides a high-stability, wear-resistant bio-based hydrophobic resin dental material, which is formed by curing the high-stability, wear-resistant bio-based hydrophobic resin composition described in the above technical solution.

[0015] The present invention also provides a method for preparing a high-stability, wear-resistant bio-based hydrophobic resin dental material, comprising the following steps: photocuring a high-stability, wear-resistant bio-based hydrophobic resin composition to obtain the high-stability, wear-resistant bio-based hydrophobic resin dental material; the wavelength of light for the photocuring is 385 to 515 nm.

[0016] Beneficial effects:

[0017] The invention provides a high-stability wear-resistant bio-based hydrophobic resin composition, which comprises the following components, measured by mass: 2-8 parts of epoxy soybean oil acrylate, 16-24 parts of triethylene glycol dimethacrylate, 5-15 parts of perfluoroalkyl acrylate, 2-15 parts of hydrophilic nano-silica, 2-15 parts of hydrophobic nano-silica, 5-15 parts of gamma-methacryloxypropyltrimethoxysilane, 0.02-0.2 parts of camphorquinone and 0.12-0.3 parts of ethyl 4-dimethylaminobenzoate. The present invention adds hydrophobic nano-silica to the resin composition to increase the compatibility of silica with the resin matrix, thereby improving the mechanical properties and cold and heat stability of the resin material and extending the service life; and the microscopic rough structure constructed by silica and the low surface energy modification by perfluoroalkyl acrylate are combined to play a synergistic role, further improving the hydrophobic stability of the resin material; at the same time, active groups exist on the surface of the hydrophobic nano-silica particles, which can improve the reaction activity of the silica nano-particles with other components; in addition, the high-stability wear-resistant bio-based hydrophobic resin composition provided by the present invention uses epoxy soybean oil acrylate as the resin matrix, replacing the commonly used bisphenol A type resin, and is more green and environmentally friendly and sustainable.

[0018] The present invention provides a high-stability wear-resistant bio-based hydrophobic resin, which is obtained by photocuring the high-stability wear-resistant bio-based hydrophobic resin composition described in the above technical scheme. In the present invention, during the photocuring process, camphorquinone generates active free radicals by photoactivation in the presence of ethyl 4-dimethylaminobenzoate, thereby initiating polymerization of carbon-carbon double bonds in epoxy soybean oil acrylate, triethylene glycol dimethacrylate, perfluoroalkyl acrylate and γ-methacryloxypropyl trimethoxysilane, and obtaining a hydrophobic self-cleaning resin dental material with a lotus leaf-like micro-nano hierarchical structure, the surface of which can retain air, and the air layer reduces the contact area between the material surface and proteins and bacteria, inhibits their adhesion, and realizes the control of dental plaque from the perspective of source etiology. At the same time, the present invention uses epoxy soybean oil acrylate as a resin matrix, replacing the commonly used bisphenol A type resin, which is more green and environmentally friendly and sustainable; and by introducing hydrophilic nano-silica and hydrophobic nano-silica, while maintaining mechanical properties and biological activity, it enhances wear resistance and cold and heat resistant hydrophobic stability, and extends the service life of the material. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required to be used in the embodiments are briefly introduced below.

[0020] Figure 1 Hydrophilic nano-silica and hydrophobic nano-silica (FAS-SiO 2) contact angle test results, where: (a) is the contact angle of 15 μL water drop on SiO 2 With FAS-SiO 2 Optical photograph of the powder tablet surface; (b) FAS-SiO 2 Static water contact angle of the powder tablet surface (water drop 5 μL);

[0021] Figure 2 The contact angle change of the resin material prepared in Examples 1 to 7 after 5000 hot and cold cycles;

[0022] Figure 3 The scanning electron microscope images of the resin dental materials prepared in Example 5 and Comparative Example 1, wherein (a1) to (a3) ​​are Comparative Example 1, and (b1) to (b3) are Example 5;

[0023] Figure 4 The figures are the dynamic behavior diagrams of water droplets in contact with the surfaces of the resin dental materials prepared in Example 5 and Comparative Example 1, wherein (a1) to (a5) are Comparative Example 1, and (b1) to (b5) are Example 5;

[0024] Figure 5 The cytocompatibility fluorescence microscopy images of the resin dental material extracts prepared in Example 5, Comparative Examples 1 to 3, and a blank control group, wherein (a1) to (a3) ​​are blank controls, (b1) to (b3) are Comparative Example 2, (c1) to (c3) are Comparative Example 3, (d1) to (d3) are Comparative Example 1, and (e1) to (e3) are Example 5;

[0025] Figure 6 Field emission scanning electron microscope images of bacteria adhesion on the surface of resin dental materials prepared in Example 5 and Comparative Examples 1 to 3, wherein (a) is Comparative Example 2, (b) is Comparative Example 3, (c) is Comparative Example 1, and (d) is Example 5. DETAILED DESCRIPTION

[0026] The invention provides a high-stability wear-resistant bio-based hydrophobic resin composition, which comprises the following components, measured by mass: 2-8 parts of epoxy soybean oil acrylate, 16-24 parts of triethylene glycol dimethacrylate, 5-15 parts of perfluoroalkyl acrylate, 2-15 parts of hydrophilic nano-silica, 2-15 parts of hydrophobic nano-silica, 5-15 parts of gamma-methacryloxypropyltrimethoxysilane, 0.02-0.2 parts of camphorquinone and 0.12-0.3 parts of ethyl 4-dimethylaminobenzoate.

[0027] In the present invention, unless otherwise specified, all raw material components are commercially available products well known to those skilled in the art.

[0028] Calculated by weight, the raw materials for preparing the high-stability wear-resistant bio-based hydrophobic resin composition provided by the present invention include 2 to 8 parts of epoxy soybean oil acrylate, specifically 3 parts, 4 parts, 5 parts, 6 parts or 7 parts.

[0029] In the present invention, the epoxy soybean oil acrylate is used as a resin matrix to replace the commonly used bisphenol A type resin, which is green, environmentally friendly and sustainable.

[0030] In the present invention, the structural formula of the epoxy soybean oil acrylate is as follows:

[0031]

[0032] Calculated by weight of the epoxy soybean oil acrylate, the raw materials for preparing the high-stability, wear-resistant bio-based hydrophobic resin composition provided by the present invention include 16 to 24 parts of triethylene glycol dimethacrylate (TEGDMA), specifically 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts or 23 parts.

[0033] In the present invention, the triethylene glycol dimethacrylate is used as a diluent monomer to undergo polymerization.

[0034] In the present invention, the structural formula of triethylene glycol dimethacrylate is as follows:

[0035]

[0036] The raw materials for preparing the high-stability wear-resistant bio-based hydrophobic resin composition provided by the present invention include 5 to 15 parts of perfluoroalkyl acrylate (FMA) based on the mass fraction of the epoxy soybean oil acrylate, and specifically can be 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts or 14 parts. In the present invention, the perfluoroalkyl acrylate (FMA) is used as a hydrophobic modifier to undergo a polymerization reaction.

[0037] In the present invention, the structural formula of the perfluoroalkyl acrylate is as follows:

[0038]

[0039] Calculated by weight of the epoxy soybean oil acrylate, the raw materials for preparing the high-stability, wear-resistant bio-based hydrophobic resin slurry provided by the present invention also include 2 to 10 parts of a diluent, specifically 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts or 9 parts; the diluent is preferably an alcohol solvent, more preferably ethanol.

[0040] Based on the mass fraction of the epoxy soybean oil acrylate, the raw materials for preparing the high-stability wear-resistant bio-based hydrophobic resin slurry provided by the present invention include hydrophilic nano-silica (SiO 2)2 to 15 parts, specifically 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 parts.

[0041] In the present invention, the hydrophilic nano-silicon dioxide is used as an inorganic filler to improve the mechanical properties of the resin while increasing the microscopic roughness of the resin.

[0042] In the present invention, the particle size of the hydrophilic nano-silica is preferably 15 to 20 nm.

[0043] Based on the mass fraction of the epoxy soybean oil acrylate, the raw materials for preparing the high-stability wear-resistant bio-based hydrophobic resin composition provided by the present invention include hydrophobic nano-silica (SiO 2 )2 to 15 parts, specifically 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 parts.

[0044] In the present invention, the hydrophobic nano-silica is used as an inorganic filler to increase the compatibility of silica with the resin matrix, thereby improving the mechanical properties and cold and heat stability of the resin material and extending the service life; at the same time, active groups exist on the surface of the hydrophobic nano-silica particles, which can increase the reaction activity of the silica nano-particles with other components.

[0045] In the present invention, the hydrophobic nano-silica is obtained by fluorination modification of hydrophilic nano-silica. In the present invention, the structural formula of the 1H,1H,2H,2H-perfluorodecyltriethoxysilane (FAS) is as follows:

[0046]

[0047] In the present invention, the hydrophobic nano-silica (FAS-SiO 2) is preferably prepared by mixing 1H, 1H, 2H, 2H-perfluorodecyl triethoxysilane, ethanol and water for hydrolysis reaction to obtain a hydrolyzate; diluting the hydrolyzate and mixing it with hydrophilic nano-silica, and then sequentially performing ultrasonic treatment and stirring, and then sequentially performing a first centrifugation, washing, a second centrifugation and drying to obtain hydrophobic nano-silica; the volume ratio of the 1H, 1H, 2H, 2H-perfluorodecyl triethoxysilane, ethanol and water is preferably 1.5:48:1.5; the water is preferably deionized water; the temperature of the hydrolysis reaction is preferably room temperature, the time is preferably 24h, and the hydrolysis reaction is preferably carried out under magnetic stirring conditions; the diluent for dilution is preferably ethanol; the volume ratio of the hydrolyzate to ethanol is preferably 50:100; the amount ratio of the hydrophilic nano-silica to the diluted hydrolyzate is preferably 0.75g:150mL; the ultrasonic bath time is preferably 24h; the hydrolysis reaction temperature is preferably 1.5:48:1.5; the water is preferably deionized water; the hydrolysis reaction temperature is preferably room temperature, the time is preferably 24h, and the hydrolysis reaction is preferably carried out under magnetic stirring conditions; the diluent for dilution is preferably ethanol; the volume ratio of the hydrolyzate to ethanol is preferably 50:100; the amount ratio of the hydrophilic nano-silica to the diluted hydrolyzate is preferably 0.75g:150mL; the ultrasonic bath time is preferably 24h; the hydrolysis reaction temperature is preferably 24h; the hydrolysis reaction temperature is preferably 24h; the hydrolysis reaction is preferably carried out under magnetic stirring conditions; the diluent for dilution is preferably ethanol; the volume ratio of the hydrolyzate to ethanol is preferably 50:100; the amount ratio of the hydrophilic nano-silica to The time is preferably 15 to 35 minutes, specifically 30 minutes; after the ultrasonic treatment, magnetic stirring is preferably performed for 24 hours, and then centrifugation is performed, and the speed of the magnetic stirring is preferably 500 rpm; the speed of the first centrifugation is preferably 1500 to 2500 rpm, specifically 2000 rpm, and the time is preferably 3 to 8 minutes, specifically 5 minutes; the washing detergent is preferably anhydrous ethanol; the speed of the second centrifugation is preferably 1500 to 2500 rpm, specifically 2000 rpm, and the time can be 3 to 8 minutes, specifically 5 minutes, and the alcohol washing centrifugation operation is preferably repeated 2 to 4 times, specifically 3 times; the drying temperature is preferably 70 to 90°C, specifically 80°C, and the time is preferably 0.2 to 1 hour, specifically 0.5 hours, and the dried product is hydrophobic nano-silica (FAS-SiO 2 ).

[0048] Calculated by weight of the epoxy soybean oil acrylate, the raw materials for preparing the high-stability, wear-resistant bio-based hydrophobic resin composition provided by the present invention include 5 to 15 parts of γ-methacryloxypropyltrimethoxysilane (KH570), specifically 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts or 14 parts.

[0049] In the present invention, the γ-methacryloxypropyltrimethoxysilane is used as a coupling agent to undergo a polymerization reaction.

[0050] In the present invention, the structural formula of the γ-methacryloxypropyltrimethoxysilane is as follows:

[0051]

[0052] Calculated by weight of the epoxy soybean oil acrylate, the raw materials for preparing the high-stability, wear-resistant bio-based hydrophobic resin slurry provided by the present invention include 0.02 to 0.2 parts of camphorquinone (CQ), specifically 0.03 parts, 0.04 parts, 0.05 parts, 0.06 parts, 0.07 parts, 0.08 parts, 0.09 parts, 0.10 parts, 0.11 parts, 0.12 parts, 0.13 parts, 0.14 parts, 0.15 parts, 0.16 parts, 0.17 parts, 0.18 parts or 0.19 parts.

[0053] In the present invention, the camphorquinone is used as a photosensitizer to generate active free radicals through photoactivation, thereby initiating a polymerization reaction.

[0054] In an embodiment of the present invention, the camphorquinone is preferably DL-camphorquinone (CAS No.: 10373-78-1).

[0055] Calculated by weight of the epoxy soybean oil acrylate, the raw materials for preparing the high-stability, wear-resistant bio-based hydrophobic resin slurry provided by the present invention include 0.12 to 0.3 parts of ethyl 4-dimethylaminobenzoate (EDMAB), specifically 0.13 parts, 0.26 parts, 0.27 parts, 0.28 parts or 0.29 parts.

[0056] In the present invention, the ethyl 4-dimethylaminobenzoate is used as a photocuring accelerator to promote camphorquinone to generate active free radicals and initiate a polymerization reaction.

[0057] The present invention provides a method for preparing a high-stability wear-resistant bio-based hydrophobic resin composition, comprising the following steps:

[0058] Epoxidized soybean oil acrylate, triethylene glycol dimethacrylate, perfluoroalkyl acrylate, diluent, hydrophilic nano-silica, hydrophobic nano-silica, gamma-methacryloxypropyltrimethoxysilane, camphorquinone and ethyl 4-dimethylaminobenzoate are mixed to obtain a highly stable and wear-resistant bio-based hydrophobic composition.

[0059] In the present invention, the mixing is preferably carried out under light-proof conditions. In an embodiment of the present invention, the mixing is preferably carried out in a brown bottle; in the present invention, the mixing time is preferably 1.5 to 6.5 hours, specifically 2 hours, 3 hours, 5.5 hours or 6 hours; the mixing temperature is preferably room temperature; the mixing method is preferably magnetic stirring mixing, and the magnetic stirring mixing speed is preferably 720 to 800 rpm / min, specifically 730 rpm / min, 750 rpm / min, 760 rpm / min or 770 rpm / min.

[0060] In the present invention, the order of mixing is preferably: first mixing epoxy soybean oil acrylate, triethylene glycol dimethacrylate, perfluoroalkyl acrylate and diluent to obtain a first mixture; second mixing the first mixture, hydrophilic nano-silica, hydrophobic nano-silica and γ-methacryloxypropyl trimethoxysilane to obtain a second mixture; third mixing the second mixture, camphorquinone and ethyl 4-dimethylaminobenzoate to obtain a bio-based hydrophobic resin composition. In the present invention, the first mixing time is preferably 0.5 to 1h, specifically 0.55h, 0.6 or 0.9h. In the present invention, the addition mode of the γ-methacryloxypropyl trimethoxysilane is preferably dropwise addition, and the present invention has no special limitation on the speed of the dropwise addition, and dropwise addition is sufficient; the second mixing time is counted from the completion of the dropwise addition of the γ-methacryloxypropyl trimethoxysilane; the second mixing time is preferably 0.5 to 1h, specifically 0.55h, 0.6h or 0.9h. In the present invention, the third mixing time is preferably 0.75 to 1.25 h, specifically 0.85 h, 1.05 h or 1.15 h.

[0061] The present invention also provides a method for preparing the high-stability, wear-resistant bio-based hydrophobic resin dental material described in the above scheme, comprising the following steps:

[0062] In the present invention, the photocuring is preferably carried out under anaerobic conditions; the wavelength of the light for the photocuring is preferably 385 to 515 nm, specifically 390 nm, 420 nm, 450 nm, 455 nm, 460 nm, 470 nm, 480 nm or 510 nm; the time for the photocuring is preferably 20 to 80 s, specifically 20 s, 40 s or 60 s; the photocuring is preferably carried out using a dental light curing lamp or a dental light curing machine. In the present invention, by irradiation with a dental light curing lamp, camphorquinone decomposes in the presence of ethyl 4-dimethylaminobenzoate to produce active free radicals, which in turn triggers polymerization of carbon-carbon double bonds in epoxy soybean oil acrylate, triethylene glycol dimethacrylate, perfluoroalkyl acrylate and γ-methacryloxypropyltrimethoxysilane to produce a highly stable, wear-resistant bio-based hydrophobic resin dental material.

[0063] The high-stability, wear-resistant bio-based hydrophobic resin dental material provided by the present invention has a lotus leaf-like hydrophobic micro-nano hierarchical structure. The surface of this structure can retain air, and the air layer reduces the contact area between the material surface and proteins and bacteria, inhibiting their adhesion, and achieving control of dental plaque from the perspective of source etiology. Compared with traditional methods for controlling dental plaque, which are all aimed at the plaque biofilm itself, the high-stability, wear-resistant bio-based hydrophobic resin dental material provided by the present invention targets the biofilm attachment substrate, inhibits protein adsorption and bacterial adhesion, and blocks its development at the very initial stage of biofilm formation. Moreover, the high-stability, wear-resistant bio-based hydrophobic resin composition provided by the present invention uses epoxy soybean oil acrylate as the resin matrix, replacing the commonly used bisphenol A type resin, which is more green and environmentally friendly and sustainable.

[0064] The present invention provides the application of the high stability wear-resistant bio-based hydrophobic resin dental material described in the above technical solution or the high stability wear-resistant bio-based hydrophobic resin dental material prepared by the above preparation method as an oral material. In the present invention, the high stability wear-resistant bio-based hydrophobic resin dental material or the high stability wear-resistant bio-based hydrophobic resin dental material prepared by the above preparation method is preferably applied to caries-prone sites, such as grooves and fissures, the neck of the teeth (especially senile neck caries) or the distal adjacent surface of the last molar. The high stability wear-resistant bio-based hydrophobic resin dental material provided by the present invention has a lotus leaf-like micro-nano structure, has good hydrophobic properties, biocompatibility and "biological cleaning" effect of inhibiting bacterial adhesion, and can be used as an oral material; moreover, the high stability wear-resistant bio-based hydrophobic resin slurry provided by the present invention can be applied in a fluid state, can achieve in-situ curing, meet the conditions for clinical application, and have advantages in special oral environments, such as as a preventive and therapeutic material for caries in patients with xerostomia.

[0065] To further illustrate the present invention, the highly stable and wear-resistant bio-based hydrophobic resin composition, dental material, preparation method and application provided by the present invention are described in detail below in conjunction with the accompanying drawings and examples, but they should not be construed as limiting the scope of protection of the present invention.

[0066] The hydrophobic nano-silicon dioxide (FAS-SiO 2 ) is obtained by modifying hydrophilic nano-silica with a particle size of 15 to 20 nm by 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane; the hydrophobic nano-silica (FAS-SiO 2) is preferably prepared by: adding 1.5 mL of 1H,1H,2H,2H-perfluorodecyltriethoxysilane (FAS) to 48 mL of ethanol and 1.5 mL of deionized water, magnetically stirring for 24 h to obtain a hydrolyzed FAS solution, diluting with 2 times the volume of ethanol to obtain a diluted FAS solution; adding 0.75 g of hydrophilic nano-silica particles with a particle size of 15 to 20 nm to the diluted FAS solution at room temperature to obtain a mixture; placing the mixture in an ultrasonic bath for 30 min, and then magnetically stirring at a speed of 500 rpm for 24 h; centrifuging the stirred mixture at 2000 rpm for 5 min, removing the supernatant, and obtaining a hydrophobic nano-silica mixture; washing the obtained hydrophobic nano-silica mixture with anhydrous ethanol, and then centrifuging at 2000 rpm for 5 min, repeating the above alcohol washing and centrifugation operation 3 times, and drying at 80° C. for 0.5 h to obtain hydrophobic nano-silica (FAS-SiO 2 ).

[0067] Example 1

[0068] (1) adding 0.5 g of epoxidized soybean oil acrylate (ESOA), 2.0 g of triethylene glycol dimethacrylate (TEGDMA), 1.0 g of perfluoroalkyl acrylate (FMA) and 0.5 g of anhydrous ethanol into a brown glass bottle, and stirring the mixture under magnetic stirring at room temperature for 0.5 h to obtain a first mixture;

[0069] (2) 0.2 g of hydrophilic nano-silicon dioxide (SiO 2 , particle size of 15-20 nm) and 0.8 g hydrophobic nano-silica (FAS-SiO 2 ) was added into the brown glass bottle, and 1.0 g of γ-methacryloxypropyltrimethoxysilane (KH570) was added dropwise under magnetic stirring. After the addition was completed, magnetic stirring was performed at room temperature for 0.5 h to obtain a second mixed material;

[0070] (3) adding 0.0105 g of camphorquinone (CQ) and 0.0245 g of ethyl 4-dimethylaminobenzoate (EDMAB) into the brown glass bottle, and magnetically stirring at room temperature for 1 h to obtain a high-stability, wear-resistant bio-based hydrophobic resin slurry;

[0071] (4) curing the resin slurry obtained in step (3) by light irradiation with a dental light curing lamp for 20 seconds at room temperature to obtain a preliminarily cured resin material;

[0072] (5) Curing the resin material obtained in step (4) by light irradiation with a dental light curing lamp under anaerobic conditions for 60 seconds to obtain a cured high-stability, wear-resistant bio-based hydrophobic resin dental material.

[0073] Embodiments 2 to 5

[0074] The only difference from Example 1 is that, based on the total mass of hydrophilic nano-silica and hydrophobic nano-silica being 1 g, the mass fractions of the hydrophobic nano-silica are 0.60 g, 0.50 g, 0.40 g, and 0.20 g.

[0075] Example 6

[0076] The only difference from Example 1 is that only 1.0 g of hydrophobic nano-silica is added.

[0077] Example 7

[0078] The only difference from Example 1 is that only 1.0 g of hydrophilic nano-silicon dioxide is added.

[0079] Example 8

[0080] (1) adding 0.5 g of epoxidized soybean oil acrylate (ESOA), 1.5 g of triethylene glycol dimethacrylate (TEGDMA), 1.0 g of perfluoroalkyl acrylate (FMA) and 0.5 g of anhydrous ethanol into a brown glass bottle, and stirring the mixture under magnetic stirring at room temperature for 0.5 h to obtain a first mixture;

[0081] (2) 0.2 g of hydrophilic nano-silicon dioxide (SiO 2 , particle size of 15-20 nm) and 0.8 g hydrophobic nano-silica (FAS-SiO 2 ) was added into the brown glass bottle, and 2.0 g of γ-methacryloxypropyltrimethoxysilane (KH570) was added dropwise under magnetic stirring, and after the addition was completed, magnetic stirring was performed at room temperature for 0.5 h to obtain a second mixed material;

[0082] (3) adding 0.0105 g of camphorquinone (CQ) and 0.0245 g of ethyl 4-dimethylaminobenzoate (EDMAB) into the brown glass bottle, and magnetically stirring at room temperature for 1 h to obtain a bio-based hydrophobic resin slurry;

[0083] (4) curing the resin slurry obtained in step (3) by light irradiation with a dental light curing lamp for 20 seconds at room temperature to obtain a preliminarily cured resin material;

[0084] (5) Curing the resin material obtained in step (4) by light irradiation with a dental light curing lamp under anaerobic conditions for 60 seconds to obtain a cured high-stability, wear-resistant bio-based hydrophobic resin dental material.

[0085] Embodiments 9-10

[0086] A high-stability, wear-resistant bio-based hydrophobic resin material was prepared according to the method of Example 8. The preparation conditions of Examples 8 to 10 are shown in Table 1.

[0087] Table 1 Preparation conditions of Examples 8 to 10

[0088] ESOA TEGDMA FMA <![CDATA[SiO 2 ]]> <![CDATA[FAS-SiO 2 ]]> KH570 CQ EDMAB Light curing Example 8 0.5g 1.5g 1.0g 0.2g 0.8 2.0g 0.0105g 0.0245g 20s Example 9 0.5g 1.0g 0.5g 0.4g 0.6 2.0g 0.0105g 0.0245g 40s Example 10 0.8g 1.0g 0.5g 0.5g 0.5 1.0g 0.0105g 0.0245g 60s

[0089] Comparative Example 1

[0090] (1) adding 0.5 g of epoxidized soybean oil acrylate (ESOA), 2.0 g of triethylene glycol dimethacrylate (TEGDMA) and 0.5 g of anhydrous ethanol into a brown glass bottle, and stirring the mixture under magnetic stirring at room temperature for 0.5 h to obtain a first mixture;

[0091] (2) adding 0.0075 g of camphorquinone (CQ) and 0.0175 g of ethyl 4-dimethylaminobenzoate (EDMAB) into the brown glass bottle, and stirring the mixture with a magnetic stirrer at room temperature for 1 h to obtain a hydrophilic resin slurry;

[0092] (3) The hydrophilic resin slurry obtained in step (2) is cured by light irradiation for 20 seconds at room temperature using a dental light curing machine to obtain a preliminarily cured hydrophilic resin dental material.

[0093] (4) Curing the bio-based hydrophilic resin slurry obtained in step (3) by light irradiation with a dental light curing lamp under anaerobic conditions for 60 seconds to obtain a cured bio-based hydrophilic resin dental material.

[0094] Comparative Example 2

[0095] The commercial resin dental material (Japanese Matsukaze reinforced flowable resin) was light-cured for 80 seconds under aerobic conditions using a dental light-curing lamp to obtain a cured commercial resin dental material.

[0096] Comparative Example 3

[0097] The commercial resin dental material (Beautiful Dentist ME light-cured pit and fissure sealant) was light-cured for 80 seconds using a dental light-curing lamp under aerobic conditions to obtain a cured commercial resin dental material.

[0098] Test Example 1

[0099] Hydrophilic nano-silica and hydrophobic nano-silica (FAS-SiO 2 ) to conduct contact angle test, and the obtained tablet surface photo is as follows Figure 1 As shown, from Figure 1 In (a), it can be seen that the water droplets on the surface of the hydrophilic nano-silica powder tablet are completely spread out, indicating that the unmodified nano-silica has hydrophilicity; Figure 1(b) SiO modified by FAS 2 The surface of the powder tablet showed spherical water droplets, and the contact angle was measured to be 156.23±3.26°, which showed that it was superhydrophobic, confirming the effect of FAS on SiO 2 The modification was successful.

[0100] Test Example 2

[0101] The static water contact angle (water drop 5 μL), microhardness (HV), and friction and wear coefficient (COF) of the resin samples of Examples 1 to 7 were tested. The results showed that the resin sample of Example 5 containing 0.8 g SiO 2 and 0.2gFAS-SiO 2 The static water contact angle of the resin material surface is greater than 150°, the hardness is the highest, and the friction coefficient is lower than the group with the highest contact angle. The specific test data are shown in Table 2.

[0102] Table 2. Static water contact angle (water drop 5 μL), microhardness (HV), friction and wear coefficient (COF) of the surfaces of Examples 1 to 7

[0103]

[0104] Test Example 3

[0105] The final resin yield was tested by Fourier transform infrared spectroscopy (FTIR, Thermo Scientific Nicolet iS50, USA) at 4000 cm -1 Up to 500cm -1 The resin samples were tested within the scanning range of infrared wavelength. The carbon-carbon double bond conversion rate of the resins prepared in Examples 1 to 7 (the formula for the carbon-carbon double bond conversion rate is (A 1 -A 2 ) / A 1 ×100%,A 1 , A 2 The absorbance or transmittance before and after the reaction are respectively, the degree of carbon-carbon double bond breakage in the raw material, representing the resin conversion rate) is compared, and the results are shown in Table 3. Example 5 contains 0.8gSiO 2 and 0.2gFAS-SiO 2 The resin material conversion rate is the highest (89.8%), and the final resin yield is the highest.

[0106] Table 3 Carbon-carbon double bond conversion rate of resin samples of Examples 1 to 7

[0107]

[0108] Test Example 4

[0109] Stability test: The resin samples obtained in Examples 1 to 7 were subjected to a hot and cold cycle test. The samples were immersed in 5°C and 55°C tap water for 15 seconds each as a cycle. The contact angles of each group before and after 5000 cycles were Figure 2 As shown in the figure, the contact angles of each group decreased after the hot and cold cycles, especially in Example 5 (SiO 2 0.80g, FAS-SiO 2 The contact angle of the resin material prepared by adding 0.20g) can be maintained at 150°, which proves that this group of resin materials has good stability.

[0110] Test Example 5

[0111] Mechanical properties test: Example 5 (SiO 2 0.80g, FAS-SiO 2 0.20g), Example 7 (adding only SiO 2 ) and the dental materials obtained in Example 1 and Comparative Example 2 were subjected to friction and wear coefficient and compression strength tests to evaluate the mechanical properties of the resin materials. As can be seen from Table 4, the hydrophobic bio-based resin dental material prepared in Example 5 of the present invention has good mechanical properties, and the friction coefficient is better than that in Example 7 (only SiO 2 ) and commercial resin dental material group (Comparative Example 2, Comparative Example 3), the compressive strength is the largest.

[0112] Table 4 Mechanical properties of different resin dental materials

[0113] Sample type Friction coefficient Compression strength(MPa) Comparative Example 1 0.22±0.08 127.25±25.23 Comparative Example 2 0.47±0.02 152.57±27.61 Comparative Example 3 0.46±0.03 162.78±20.94 Example 5 0.35±0.07 168.37±16.06 Example 7 0.43±0.02 128.22±31.91

[0114] Test Example 6

[0115] Taking Example 5 as an example, the surface morphology and performance of the high-stability, wear-resistant bio-based hydrophobic resin dental material prepared by the present invention were tested.

[0116] (1) Micromorphology and surface wettability

[0117] Figure 3 The following are scanning electron micrographs of the resin dental materials prepared in Example 5 and Comparative Example 1, wherein (a1) to (a3) ​​are Comparative Example 1, and (b1) to (b3) are Example 5. Figure 3 As can be seen from (b1) to (b3) in the figure, the surface of the bio-based hydrophobic resin dental material prepared in Example 5 of the present invention has many micron-scale protrusions, which are composed of many nano-scale SiO 2 The particles form a hydrophobic surface with a micro-nano structure (contact angle greater than 150°). Compared with the smoother hydrophilic resin dental material Figure 3Compared with ((a1)~(a3), the contact angle is about 80°), the surface of this micro-nanostructure can retain air. The air layer reduces the contact area between the material surface and proteins and bacteria, inhibits their adhesion, and achieves control of dental plaque from the perspective of source etiology.

[0118] (2) Dynamic behavior of material surface contact

[0119] Test method: Place a 5 μL water droplet on the surface of the resin dental material prepared in Example 5 and Comparative Example 1, move the syringe downward by hand, and return upward after contacting the surface of the resin dental material.

[0120] Figure 4 The following are the dynamic behavior diagrams of water droplets contacting the surfaces of the resin dental materials prepared in Example 5 and Comparative Example 1, wherein (a1) to (a5) are Comparative Example 1, and (b1) to (b5) are Example 5. Figure 4 It can be seen from (b1) to (b5) in that when the bio-based hydrophobic resin dental material prepared in Example 5 of the present invention comes into contact with a water droplet, the water droplet is deformed and the water droplet does not adhere to the surface. The air layer between the surface of the hydrophobic resin dental material and the water droplet reduces the adhesion between the material and the water droplet. Figure 4 It can be seen from (a1) to (a5) that when the bio-based hydrophilic resin dental material comes into contact with a water droplet, the water droplet immediately adheres to its surface and spreads out, and the adhesion between the bio-based hydrophilic resin dental material and the water droplet is strong.

[0121] (3) Biocompatibility

[0122] Test method: The bio-based hydrophobic resin dental material prepared in Example 5, the bio-based hydrophilic resin dental material prepared in Comparative Example 1, and the cured commercial resin dental materials prepared in Comparative Examples 2 and 3 were placed in 90% MEM + 10% fetal bovine serum to prepare extracts. 90% MEM + 10% fetal bovine serum was used as a blank control group.

[0123] Mouse fibroblasts (L929) were co-cultured with the prepared extract for 1 day, 3 days and 5 days, respectively, and the cell growth state and proliferation were observed under a fluorescence microscope after staining with rhodamine 123.

[0124] Figure 5 The cytocompatibility fluorescence microscopy images of the resin dental material extracts prepared in Example 5, Comparative Examples 1 to 3, and the blank control group, wherein (a1) to (a3) ​​are the blank control group, (b1) to (b3) are Comparative Example 2, (c1) to (c3) are Comparative Example 3, (d1) to (d3) are Comparative Example 1, and (e1) to (e3) are Example 5. Figure 5From (e1) to (e3), it can be seen that the cell proliferation density and cell morphology of the bio-based hydrophobic resin dental material experimental group prepared in Example 5 of the present invention are similar to those of the blank control group and the hydrophilic resin dental material group (Comparative Example 1), and are much better than those of the commercial resin dental material groups (Comparative Example 2 and Comparative Example 3). This shows that compared with the two commercial resin dental materials and the blank control group, the bio-based hydrophobic resin dental material prepared in the present invention has good biocompatibility.

[0125] (4) Surface bacterial adhesion

[0126] Test method: The bio-based hydrophobic resin dental material prepared in Example 5, the bio-based hydrophilic resin dental material prepared in Comparative Example 1, and the cured commercial resin dental materials prepared in Comparative Examples 2 and 3 were co-cultured with Streptococcus mutans for 24 hours, and then sampled, rinsed, fixed, dried, and gold-sprayed, and the bacterial adhesion on the sample surface was observed using a field emission scanning electron microscope.

[0127] Figure 6 Field emission scanning electron microscope images of bacteria adhesion on the surface of the resin dental materials prepared in Example 5 and Comparative Examples 1 to 3, wherein (a) is Comparative Example 2, (b) is Comparative Example 3, (c) is Comparative Example 1, and (d) is Example 5. Figure 6 As can be seen from (d), there are only a small amount of bacteria on the surface of the bio-based hydrophobic resin dental material prepared in Example 5 of the present invention, which proves that the material can effectively inhibit bacterial adhesion; while a large amount of mutans Streptococcus adheres to the surfaces of the commercial resin dental material group (Comparative Example 2, Comparative Example 3) and the bio-based hydrophilic resin dental material group (Comparative Example 1) to varying degrees. This shows that compared with the two commercial resin dental materials, the high-stability and wear-resistant bio-based hydrophobic resin dental material prepared by the present invention can effectively inhibit bacterial adhesion and has a good "biological cleaning" effect.

[0128] In summary, the high-stability, wear-resistant bio-based hydrophobic resin dental material prepared by the present invention has a lotus leaf-like micro-nano structure, good hydrophobic properties, biocompatibility and a "biological cleaning" effect of inhibiting bacterial adhesion. It can be applied to caries-prone sites, such as grooves and fissures, the neck of teeth (especially senile cervical caries) or the distal adjacent surfaces of the last molars, as well as some special oral environments, for example, it has the effect of preventing and treating caries in patients with xerostomia.

[0129] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. People can also obtain other embodiments based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A highly stable and wear-resistant bio-based hydrophobic resin composition, characterized in that: The invention comprises the following components in parts by mass: 2 to 8 parts of epoxy soybean oil acrylate, 16 to 24 parts of triethylene glycol dimethacrylate, 5 to 15 parts of perfluoroalkyl acrylate, 2 to 15 parts of hydrophilic nano-silica, 2 to 15 parts of hydrophobic nano-silica, 5 to 15 parts of γ-methacryloxypropyltrimethoxysilane, 0.02 to 0.2 parts of camphorquinone and 0.12 to 0.3 parts of ethyl 4-dimethylaminobenzoate.

2. The high stability and wear-resistant bio-based hydrophobic resin composition according to claim 1, characterized in that: Taking the total mass of the hydrophilic nano-silicon dioxide and the hydrophobic nano-silicon dioxide as 100%, the mass fraction of the hydrophobic nano-silicon dioxide is 20-80%.

3. The high stability, wear-resistant bio-based hydrophobic resin composition according to claim 1 or 2, characterized in that: The particle size of the hydrophilic nano-silicon dioxide is 15 to 20 nm.

4. The high stability, wear-resistant bio-based hydrophobic resin composition according to claim 1 or 2, characterized in that: The hydrophobic nano-silica is obtained by modifying the hydrophilic nano-silica with 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane.

5. The high stability and wear-resistant bio-based hydrophobic resin composition according to claim 1 or 2, characterized in that: The invention also comprises 2 to 10 parts of a diluent, wherein the diluent is an alcohol solvent.

6. The method for preparing the high-stability wear-resistant bio-based hydrophobic resin composition according to claim 5, characterized in that: The following steps are involved: Epoxidized soybean oil acrylate, triethylene glycol dimethacrylate, perfluoroalkyl acrylate, diluent, hydrophilic nano-silica, hydrophobic nano-silica, γ-methacryloxypropyltrimethoxysilane, camphorquinone and ethyl 4-dimethylaminobenzoate are mixed to obtain the high-stability wear-resistant bio-based hydrophobic resin composition.

7. The preparation method according to claim 6, characterized in that: The mixing is carried out under light-proof conditions; the mixing time is 1.5 to 6.5 hours; the mixing method is magnetic stirring mixing, and the speed of the magnetic stirring mixing is 720 to 800 rpm / min.

8. A highly stable and wear-resistant bio-based hydrophobic resin dental material, characterized in that: The composition is formed by curing the high-stability, wear-resistant bio-based hydrophobic resin composition described in any one of claims 1 to 5 or the high-stability, wear-resistant bio-based hydrophobic resin composition prepared by the preparation method described in any one of claims 6 to 7.

9. The method for preparing the high-stability, wear-resistant bio-based hydrophobic resin dental material according to claim 8, characterized in that: The following steps are involved: The high-stability and wear-resistant bio-based hydrophobic resin composition is photocured to obtain the high-stability and wear-resistant bio-based hydrophobic resin dental material; the light wavelength of the photocuring is 385-515nm.

10. Use of the high-stability, wear-resistant bio-based hydrophobic resin dental material according to claim 8 or the high-stability, wear-resistant bio-based hydrophobic resin dental material prepared by the preparation method according to claim 9 as an oral material.

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