Fluorine-containing denture resin material for preventing dental caries and method for preparing the same

Abstract

The application discloses a fluorine-added denture resin material for preventing dental caries and a preparation method thereof, and relates to the technical field of denture materials. The fluorine-added denture resin material for preventing dental caries comprises the following components in parts by weight: modified polymethyl methacrylate 59.5-76.5 parts; self-repairing microcapsules 8-10 parts; GA@HBN antibacterial composite material 3.5-4.5 parts; nano ZrO2 22.4-3.6 parts; stabilizer 1-1.2 parts; dispersant 0.16-0.24 parts; compatibilizer 0.25-0.35 parts; initiator 0.7-0.9 parts; and antioxidant 0.08-0.12 parts. The fluorine-added denture resin material for preventing dental caries prepared by the application has the advantages of self-repairing ability against micro-cracks, wear resistance, prevention of dental caries of surrounding natural teeth in an oral environment, antibacterial property, anti-dyeing property, near-natural tooth color and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of denture materials, in particular to a fluorine-added denture resin material for preventing dental caries and a preparation method thereof. BACKGROUND

[0002] At present, although denture resin materials have been widely used in the field of oral repair, they still face multiple difficulties. The mechanical properties (such as bending strength and wear resistance) of traditional resin substrates are difficult to match the biomechanical properties of natural teeth for a long time, especially under the repeated action of masticatory stress, which is easy to cause microcracks or fractures, resulting in the shortening of the service life of the restoration. At the same time, the existing materials have insufficient antibacterial properties, which cannot effectively inhibit the colonization of oral pathogenic bacteria (such as Streptococcus mutans), which may cause secondary caries or gingival inflammation, threatening the oral health of patients. In terms of aesthetics, most resin substrates have weak anti-staining ability and are easy to cause color shift after long-term contact with pigment substances such as coffee and tea. In addition, the existing materials lack self-repairing function, and once micro-damage occurs due to stress or aging, artificial intervention is required for repair, which significantly increases the clinical maintenance cost.

[0003] Although some modified resins have made progress in mechanical enhancement or caries prevention by adding inorganic fillers or antibacterial agents (such as nano-silver and fluoride) in recent years, these improvements often come at the expense of other properties. For example, high proportion of fillers increases the brittleness of the material, while the slow-release efficiency and long-term effectiveness of antibacterial components are still insufficient, and may cause cytotoxicity risk. In the field of self-repairing, the existing light / heat responsive systems are limited by the complexity of the oral environment, making it difficult to achieve precise triggering and efficient healing. Therefore, there is an urgent need for a denture resin material with excellent mechanical properties, excellent antibacterial properties, self-repairing ability, anti-staining ability, near-natural tooth color, and the ability to prevent natural tooth caries. SUMMARY

[0004] The purpose of the present application is to provide a fluorine-added denture resin material for preventing dental caries and a preparation method thereof to solve the problems raised in the background art.

[0005] To achieve the above-mentioned purpose, the present application provides the following technical solutions:

[0006] A fluorine-added denture resin material for preventing dental caries, comprising the following raw material components by weight fraction:

[0007] Modified polymethyl methacrylate 59.5-76.5 parts;

[0008] Self-repairing microcapsules 8-10 parts;

[0009] GA@HBN antibacterial composite material 3.5-4.5 parts;

[0010] Nano ZrO22.4-3.6 parts;

[0011] Stabilizer 1-1.2 parts;

[0012] Dispersant 0.16-0.24 parts;

[0013] Compatibility agent 0.25-0.35 parts;

[0014] Initiator 0.7-0.9 parts;

[0015] Antioxidant 0.08-0.12 parts.

[0016] Further, the modified polymethyl methacrylate is a PMMA-HEMA copolymer modified by toughening copolymerization of hydroxyethyl methacrylate, and the content of hydroxyethyl methacrylate is 4-6%, and the specific preparation steps are as follows:

[0017] Methyl methacrylate, hydroxyethyl methacrylate, azobisisobutyronitrile and dibutyl hydroxytoluene are added to a three-necked flask and mixed, heated to 60°C under nitrogen atmosphere, and heated in a water bath at a stirring speed of 300r / min for 40-60min, and then cooled to room temperature to obtain modified polymethyl methacrylate.

[0018] Further, the mass ratio of methyl methacrylate, hydroxyethyl methacrylate, azobisisobutyronitrile and dibutyl hydroxytoluene is 95:5:0.5:0.1.

[0019] It should be noted that the hydroxyl group of hydroxyethyl methacrylate (HEMA) copolymerizes with MMA to form a PMMA-HEMA random copolymer, which on the one hand, destroys the regularity of the PMMA molecular chain, reduces the crystallinity, and improves the toughness, and at the same time, the hydroxyl group of HEMA forms intermolecular hydrogen bonds with the PMMA segment, disperses the stress, and cooperates with the self-repairing microcapsule to inhibit the expansion of microcracks; on the other hand, the introduction of hydroxyl group improves the hydrophilicity, and the hydrophilic surface is more difficult for bacteria and fungi to adhere, which cooperates with the GA@HBN antibacterial composite to improve the antibacterial performance.

[0020] Further, the preparation method of the self-repairing microcapsule is as follows:

[0021] Urea, ammonium chloride and deionized water are added to an ethylene maleic anhydride aqueous solution, the pH is adjusted to 2.4-3.5, and stirring is carried out at a speed of 150r / min for 30min, the core material and polymerization inhibitor are added dropwise to the above obtained solution, and stirring is carried out at a speed of 400r / min for 15min, the formaldehyde solution is slowly added, the temperature is raised to 55°C at a rate of 10°C / min, and stirring is continued for 4h, and then the self-repairing microcapsule is obtained after washing and drying;

[0022] Further, the mass fraction of ethylene maleic anhydride in the ethylene maleic anhydride aqueous solution is 2.5%; the core material is triethylene glycol dimethacrylate with a mass fraction of 99% and N,N-bis(2-hydroxyethyl)-p-toluidine with a mass fraction of 1%; the mass fraction of formaldehyde in the formaldehyde solution is 37%; and the polymerization inhibitor is hydroquinone.

[0023] Further, the use amount ratio of the ethylene maleic anhydride aqueous solution, urea, ammonium chloride, deionized water, core material, polymerization inhibitor and formaldehyde solution is (20-30) mL:(2-3) g:(0.2-0.3) g:100 mL:(48-72) mL:(25.2-37.8) mg:(4.64-6.96) mL.

[0024] It should be noted that the self-repairing microcapsule is formed by the interface polycondensation reaction of urea and formaldehyde catalyzed by ammonium chloride to form methyl urea, and further polycondensation to form polyurea formaldehyde (PUF) three-dimensional polymer network. The polyurea formaldehyde is a shell material, triethylene glycol dimethacrylate monomer (TEGDMA) is a healing agent core material, and N,N-bis(2-hydroxyethyl)-p-toluidine (DHEPT) is a promoter. On the one hand, when the material produces microcracks due to mechanical or thermal stress, the stress concentration at the crack tip causes the microcapsule shell layer to break (the fracture toughness of the PUF shell is lower than that of the resin matrix, which can ensure that the crack preferentially passes through the microcapsule breakage), releasing TEGDMA and DHEPT into the crack gap. TEGDMA quickly infiltrates and fills the crack area due to its low viscosity characteristics, and DHEPT activates the premixed benzoyl peroxide (BPO) initiator in the resin matrix, triggering the free radical polymerization reaction of TEGDMA, forming a cross-linked polymer network, achieving in-situ repair of the crack. The process delays crack propagation through a dynamic repair mechanism, and the polymer bridge formed after the repair agent polymerizes bridges the two sides of the crack, reconstructing the material continuity and dispersing the stress. On the other hand, the addition of microcapsules also improves the toughness of the material through the "crack deflection effect / pinning effect" — when the crack propagation path encounters a microcapsule, its interface prompts the crack to detour or bifurcate, extending the propagation distance and consuming more fracture energy. At the same time, the compatibility design of the microcapsule shell layer and the resin matrix ensures uniform dispersion and avoids defects caused by agglomeration. This system, through the synergistic effect of damage-responsive repair and energy dissipation network, endows the denture resin material with dynamic crack resistance, which can prolong the service life of the denture under cyclic loading.

[0025] Further, the preparation steps of the GA@HBN antibacterial composite material are as follows:

[0026] A1, hexagonal boron nitride powder was added into an aqueous ethanol solution, and was stirred at a speed of 200 r / min for 30 min to be initially dispersed, was transferred into an ultrasonic cleaner, and was ultrasonically treated for 24 h, was centrifuged at a speed of 3000 r / min for 30 min, the precipitate was discarded, and the supernatant was collected and frozen to obtain boron nitride;

[0027] Further, the volume ratio of ethanol to water in the aqueous ethanol solution in step A1 was 1:1, and the usage ratio of the hexagonal boron nitride powder to the aqueous ethanol solution was 1 g:100 mL;

[0028] A2, the boron nitride was dispersed in deionized water to obtain a boron nitride dispersion;

[0029] Further, the usage ratio of the boron nitride to the deionized water in step A2 was 1 g:100 mL;

[0030] A3, gallic acid was dissolved in deionized water to obtain a GA solution, and was stirred at a speed of 500 r / min for 10 min, the boron nitride dispersion obtained in step A2 was added, and was stirred at a speed of 200 r / min at 80℃ for 24 h, was centrifuged at a speed of 5000 r / min for 15 min, the precipitate was collected, and was freeze-dried to obtain a GA@HBN antibacterial composite material;

[0031] Further, the usage ratio of gallic acid to deionized water in step A3 was 1 g:50 mL, and the volume ratio of the GA solution to the boron nitride dispersion was 14:3.

[0032] It should be noted that as a two-dimensional nanomaterial, nano-boron nitride is uniformly dispersed in the resin matrix due to its high modulus and layered structure, and the material rigidity is improved through stress transfer and crack pinning effect. Its lamellar structure can effectively block the crack propagation path, and at the same time dissipate impact energy through interface friction, significantly improve the bending strength and impact resistance. The planar orientation characteristics of nanosheets can also form a self-lubricating layer during wear to improve wear resistance. Gallic acid (GA) is a flavonoid compound with good antibacterial activity. On the one hand, GA can manifest its antibacterial activity by destroying the integrity of fungal cell membranes, inducing membrane lipid peroxidation through phenolic hydroxyl groups, and inhibiting the expression of key genes in Candida albicans hyphae transformation; on the other hand, GA and nano-boron nitride synergistically produce reactive oxygen species, change the mitochondrial transmembrane potential, and induce mitochondrial dysfunction, and the sharp edges of nano-boron nitride can physically pierce the cell membrane, forming a "nano-knife" effect; GA forms hydrogen bonds with the surface of nano-boron nitride through phenolic hydroxyl groups, achieving stable loading, and the two-dimensional structure of nano-boron nitride provides a high specific surface area carrier for GA, delaying the dissolution of active ingredients and prolonging the antibacterial time. At the same time, the interface modification of GA improves the dispersibility of BNNS in the resin, reducing the stress concentration defects caused by nanosheet aggregation. The GA@HBN antibacterial composite material constructs a dual protection system of physical barrier and chemical biological killing, improving the mechanical properties of the denture resin material while realizing long-acting antifungal function.

[0033] Further, the stabilizer is a polyvinyl alcohol emulsifier.

[0034] Further, the dispersant is titanium ester coupling agent NDZ-201.

[0035] It should be noted that the titanium ester coupling agent can improve the dispersibility of nano-ZrO2. Nano-ZrO2 can disperse stress concentration on the one hand, and improve the mechanical properties of the denture resin material in cooperation with other materials; on the other hand, it can adjust the refractive index to simulate the luster of enamel, and cooperate with the fluorine-containing layer to resist staining.

[0036] Further, the compatibilizer is KH-570 silane coupling agent.

[0037] It should be noted that the KH-570 silane coupling agent can improve the interfacial compatibility of the GA@HBN antibacterial composite material and the resin.

[0038] Further, the initiator is benzoyl peroxide.

[0039] It should be noted that when microcracks occur, stress concentration causes the self-repairing microcapsule PUF shell to rupture and release TEGDMA and DHEPT, and DHEPT promotes the polymerization of benzoyl peroxide (BPO) and TEGDMA to form a cross-linked polymer network, repairing the cracks in situ.

[0040] Further, the antioxidant is 2,6-di-tert-butyl-p-cresol.

[0041] A preparation procedure of the fluorine-added denture resin material for preventing dental caries is as follows:

[0042] S1, the modified polymethyl methacrylate, initiator and antioxidant are weighed according to the weight parts, added to the planetary mixer, stirred at 25℃ with a speed of 200r / min for 10-15min; the GA@HBN antibacterial composite material and the compatibilizer are weighed and added according to the weight parts, stirred at a speed of 200r / min for 1-3min, the nano ZrO2 and the dispersing agent are added, stirred at a speed of 200r / min for 1-3min; the speed is reduced to 50r / min, the self-repairing microcapsule and the stabilizer are weighed and added according to the weight parts, stirred for 3-5min, and the premix is obtained;

[0043] S2, the premix is transferred to a three-roll mill, the roll spacing is 50μm, the roll speed ratio is 1:3:9, and the circulation is 3 times, and the premix is obtained; the premix is placed in a vacuum defoaming machine, the vacuum degree is-0.095MPa, 25℃, and the defoaming is carried out for 15min, and the crude resin material is obtained;

[0044] Further, the bubble residue in the crude resin material in step S2 is less than 0.1%;

[0045] S3, the crude resin material is poured into a resin tank, the DLP light curing printer is turned on, the 405nm light source is selected, the light intensity is set to 15mW / cm 2 , the designed model file is imported, the layer thickness is set to 50μm, after printing, the model is placed in 40℃ warm water together with water-soluble PVA support, and soaked for 30min until the support is dissolved;

[0046] Further, in step S3, the infrared thermal imager is aimed at the printing area to ensure that the temperature is lower than 60℃, if the temperature is too high, the printing is paused and the light intensity is reduced or the interlayer cooling time is increased;

[0047] S4, the fluorosilane solution is configured, the printed part is completely immersed in the fluorosilane solution, and is placed at 25℃ for 30min, then is placed in a 60℃ oven for drying for 30-60min, the dried model is placed in a ultraviolet curing box, the wavelength is set to 365nm, the intensity is set to 8-12mW / cm 2 , and is irradiated for 15-20min, is placed in a 50℃ oven for 40-80min, the oven is heated to 80℃ and is placed for 90-150min, and is naturally cooled to room temperature, and the fluorine-added denture resin material for preventing dental caries is obtained.

[0048] Further, in step S4, 100mL of anhydrous ethanol is taken, 0.1g of perfluorooctyltriethoxysilane is added, stirred for 5min until dissolved, and the fluorosilane solution is configured.

[0049] It should be noted that the prepared fluorosilane solution needs to be sealed in the dark, and the effect of present preparation and present use is better.

[0050] Compared with the prior art, the present application has the following beneficial effects:

[0051] The modified polymethyl methacrylate can improve the toughness of the denture resin material, reduce brittleness, improve hydrophilicity, and reduce bacterial adhesion; the self-repairing microcapsule can improve the mechanical properties of the denture resin material and endow the denture resin material with self-repairing ability; the GA@HBN antibacterial composite material can greatly improve the antibacterial performance of the denture resin material while improving the mechanical properties of the denture resin material; the nano ZrO2 improves the mechanical properties of the denture resin material, adjusts the refractive index, simulates the luster of dental enamel, and improves the aesthetic degree; the fluorosilane releases F - On the one hand, it promotes the remineralization of dental enamel and forms a hydrophobic layer to reduce pigment adsorption, and on the other hand, it can inhibit the acid production of Streptococcus mutans and inhibit bacterial activity, thereby indirectly improving the antibacterial performance.

[0052] The fluorine-added denture resin material prepared by the present application has the advantages of anti-microcrack self-repairing ability, wear resistance, prevention of caries of surrounding natural teeth in the oral environment, antibacterial property, anti-dyeing, near-natural tooth color, etc., and has great potential in the field of oral repair materials. DETAILED DESCRIPTION

[0053] The technical solutions in the embodiments of the present application will be described below in a clear and complete manner. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0054] (1) The preparation steps of the modified polymethyl methacrylate are as follows:

[0055] 95g of methyl methacrylate, 5g of hydroxyethyl methacrylate, 0.5g of azobisisobutyronitrile and 0.1g of dibutyl hydroxytoluene are added to a three-necked flask and mixed, heated to 60℃ under nitrogen atmosphere, and heated in a water bath at a stirring speed of 300r / min for 40-60min, and then cooled to room temperature to obtain the modified polymethyl methacrylate.

[0056] (2) The preparation method of the self-repairing microcapsule is as follows:

[0057] In 25 mL of ethylene maleic anhydride aqueous solution with a mass fraction of 2.5% of ethylene maleic anhydride, 2.5 g of urea, 0.25 g of ammonium chloride and 100 mL of deionized water were added, the pH was adjusted to 2.4-3.5, and stirring was carried out at a speed of 150 r / min for 30 min. 31.185 g of triethylene glycol dimethacrylate, 0.315 g of N,N-bis(2-hydroxyethyl)-p-toluidine and 5.8 mL of hydroquinone were added dropwise to the above obtained solution, stirring was carried out at a speed of 400 r / min for 15 min, a formaldehyde solution with a mass fraction of 37% of formaldehyde was slowly added, the temperature was raised to 55°C at a rate of 10°C / min, and stirring was continuously carried out for 4 h. After passing, washing and drying, self-repairing microcapsules were obtained.

[0058] (3) The preparation steps of the GA@HBN antibacterial composite material are as follows:

[0059] A1, 0.5 g of hexagonal boron nitride powder was added to 50 mL of ethanol aqueous solution with a mass fraction of 44% of ethanol, and magnetic stirring was carried out at a speed of 200 r / min for 30 min to preliminarily disperse, and then it was transferred to an ultrasonic cleaner for ultrasonic treatment for 24 h, centrifuged at a speed of 3000 r / min for 30 min, the precipitate was discarded, and the supernatant was collected and frozen to obtain boron nitride;

[0060] A2, 0.3 g of boron nitride was dispersed in 30 mL of deionized water to obtain a boron nitride dispersion;

[0061] A3, 2.8 g of gallic acid was dissolved in 140 mL of deionized water to obtain a GA solution, magnetic stirring was carried out at a speed of 500 r / min for 10 min, 30 mL of the boron nitride dispersion obtained in step A2 was added, and magnetic stirring was carried out at a speed of 200 r / min for 24 h at 80°C, centrifugation was carried out at a speed of 5000 r / min for 15 min, the precipitate was collected, and freeze-drying was carried out to obtain a GA@HBN antibacterial composite material;

[0062] Example 1

[0063] A fluorine-containing denture resin material for preventing dental caries, which comprises the following raw material components in parts by weight:

[0064] Modified polymethyl methacrylate (content of hydroxyethyl methacrylate is 5%) 68 parts;

[0065] Self-repairing microcapsules 9 parts;

[0066] GA@HBN antibacterial composite material 4 parts;

[0067] Nano ZrO2 3 parts;

[0068] Polyvinyl alcohol emulsifier 1.1 parts;

[0069] Titanate coupling agent NDZ-201 0.2 parts;

[0070] Silane coupling agent KH-570 0.3 parts;

[0071] Benzoyl peroxide 0.8 parts;

[0072] 2,6-di-tert-butyl-p-cresol 0.1 parts.

[0073] A preparation process of a fluorine-added denture resin material for preventing dental caries is as follows:

[0074] S1, the modified polymethyl methacrylate, benzoyl peroxide and 2,6-di-tert-butyl-p-cresol are weighed according to the weight parts, added to a planetary mixer, stirred at 25℃ at a speed of 200r / min for 12min; the GA@HBN antibacterial composite material and the silane coupling agent KH-570 are weighed and added according to the weight parts, stirred at a speed of 200r / min for 3min, the nano ZrO2 and the titanate coupling agent NDZ-201 are added, stirred at a speed of 200r / min for 3min; the speed is reduced to 50r / min, the self-repairing microcapsules and the polyvinyl alcohol emulsifier are weighed and added according to the weight parts, stirred for 3min, and a premix is obtained;

[0075] S2, the premix is transferred to a three-roll grinder, the roll spacing is 50μm, the roll speed ratio is 1:3:9, and the cycle is 3 times, to obtain a premix; the premix is placed in a vacuum degassing machine, the vacuum degree is-0.095MPa, 25℃, and the degassing time is 15min, to obtain a crude resin material;

[0076] S3, the crude resin material is poured into a resin tank, a DLP light curing printer is turned on, a 405nm light source is selected, the light intensity is set to 15mW / cm 2 , a designed model file is imported, the layer thickness is set to 50μm, after printing, the model is placed in 40℃ warm water together with water-soluble PVA support, soaked for 30min until the support is dissolved, an infrared thermal imager is aimed at the printing area to ensure that the temperature is lower than 60℃, if the temperature is too high, the printing is paused and the light intensity is reduced or the interlayer cooling time is increased;

[0077] S4, 100mL of anhydrous ethanol is taken, 0.1g of perfluorooctyltriethoxysilane is added, stirred for 5min until dissolved, and a fluorosilane solution is prepared, the printed part is completely immersed in the fluorosilane solution, and is placed at 25℃ for 30min, then is placed in a 60℃ oven for drying for 45min, the dried model is placed in a UV curing box, set to 365nm wavelength and 10mW / cm 2 intensity, irradiated for 18min, placed in a 50℃ oven for 1h, the oven is heated to 80℃ and placed for 2h, and naturally cooled to room temperature, to obtain a fluorine-added denture resin material for preventing dental caries.

[0078] Example 2

[0079] A fluorine-added denture resin material for preventing dental caries comprises the following raw material components by weight fraction:

[0080] Modified polymethyl methacrylate (hydroxyethyl methacrylate content of 5%) 59.5 parts;

[0081] Self-repairing microcapsules 8 parts;

[0082] GA@HBN antibacterial composite 3.5 parts;

[0083] Nano ZrO2 22.4 parts;

[0084] Polyvinyl alcohol emulsifier 1 part;

[0085] Titanate coupling agent NDZ-201 0.16 parts;

[0086] KH-570 silane coupling agent 0.25 parts;

[0087] Benzoyl peroxide 0.7 parts;

[0088] 2,6-di-tert-butyl-p-cresol 0.08 parts.

[0089] The preparation steps of a fluorine-added denture resin material for preventing dental caries are as follows:

[0090] S1, weigh the modified polymethyl methacrylate, benzoyl peroxide and 2,6-di-tert-butyl-p-cresol by weight fraction, add them to a planetary mixer, stir at 25°C at a speed of 200 r / min for 12 min; weigh and add the GA@HBN antibacterial composite and the KH-570 silane coupling agent by weight fraction, stir at a speed of 200 r / min for 3 min, add the nano ZrO2 and the titanate coupling agent NDZ-201, stir at a speed of 200 r / min for 3 min; reduce the speed to 50 r / min, weigh and add the self-repairing microcapsules and the polyvinyl alcohol emulsifier by weight fraction, stir for 3 min to obtain a premix;

[0091] S2, transfer the premix to a three-roll grinder, with a roll spacing of 50 μm, a roll speed ratio of 1:3:9, and a cycle of 3 times to obtain a premix; place the premix in a vacuum degassing machine, with a vacuum degree of -0.095 MPa, at 25°C, and degas for 15 min to obtain a crude resin material;

[0092] S3, pour the crude resin material into a resin tank, turn on the DLP photocuring printer, select a 405 nm light source, and set the light intensity to 15 mW / cm 2, import the designed model file, set the layer thickness to 50μm, after printing, put the model together with the water-soluble PVA support into 40℃ warm water, soak for 30min until the support dissolves, aim the infrared thermal imager at the printing area to ensure the temperature is below 60℃, if it exceeds, pause the printing and reduce the light intensity or increase the interlayer cooling time;

[0093] S4, take 100mL of anhydrous ethanol, add 0.1g of perfluorooctyltriethoxysilane, stir for 5min until dissolved, configure to obtain a fluorosilane solution, completely immerse the printed piece in the fluorosilane solution, stand at 25℃ for 30min, put it into a 60℃ oven to dry for 45min, put the dried model into a UV curing box, set the wavelength to 365nm, 10mW / cm 2 intensity, irradiate for 18min, stand in a 50℃ oven for 1h, raise the oven temperature to 80℃ and stand for 2h, naturally cool to room temperature, to obtain a fluoride-containing denture resin material for preventing dental caries.

[0094] Example 3

[0095] A fluoride-containing denture resin material for preventing dental caries, including the following raw material components by weight fraction:

[0096] Modified polymethyl methacrylate (content of hydroxyethyl methacrylate is 5%) 76.5 parts;

[0097] Self-repairing microcapsules 10 parts;

[0098] GA@HBN antibacterial composite 4.5 parts;

[0099] Nano ZrO2 23.6 parts;

[0100] Polyvinyl alcohol emulsifier 1.2 parts;

[0101] Titanate coupling agent NDZ-201 0.24 parts;

[0102] KH-570 silane coupling agent 0.35 parts;

[0103] Benzoyl peroxide 0.9 parts;

[0104] 2,6-di-tert-butyl-p-cresol 0.12 parts.

[0105] The preparation steps of a fluoride-containing denture resin material for preventing dental caries are as follows:

[0106] S1, weigh modified polymethyl methacrylate, benzoyl peroxide and 2,6-di-tert-butyl-p-cresol by weight parts, add to a planetary mixer, stir at 25℃ at a speed of 200r / min for 12min; weigh and add GA@HBN antibacterial composite and KH-570 silane coupling agent by weight parts, stir at a speed of 200r / min for 3min, add nano ZrO2 and titanate coupling agent NDZ-201, stir at a speed of 200r / min for 3min; reduce the speed to 50r / min, weigh and add self-repairing microcapsules and polyvinyl alcohol emulsifier by weight parts, stir for 3min to obtain a premix;

[0107] S2, transfer the premix to a three-roll mill, the roll spacing is 50μm, the roll speed ratio is 1:3:9, circulate 3 times to obtain a premix; place the premix in a vacuum defoaming machine, the vacuum degree is-0.095MPa, 25℃, defoam for 15min to obtain a crude resin material;

[0108] S3, pour the crude resin material into a resin tank, turn on the DLP light curing printer, select a 405nm light source, set the light intensity to 15mW / cm 2 , import the designed model file, set the layer thickness to 50μm, after printing, place the model together with the water-soluble PVA support in 40℃ warm water, soak for 30min until the support dissolves, aim the infrared thermal imager at the printing area to ensure that the temperature is below 60℃, if the temperature is too high, pause the printing and reduce the light intensity or increase the interlayer cooling time;

[0109] S4, take 100mL of anhydrous ethanol, add 0.1g of perfluorooctyltriethoxysilane, stir for 5min until dissolved, configure to obtain a fluorosilane solution, completely immerse the printed piece in the fluorosilane solution, stand for 30min at 25℃, place in a 60℃ oven to dry for 45min, place the dried model in a UV curing box, set the wavelength to 365nm, the intensity to 10mW / cm 2 , irradiate for 18min, stand in a 50℃ oven for 1h, increase the oven temperature to 80℃ and stand for 2h, naturally cool to room temperature to obtain the fluoride-containing denture resin material for preventing dental caries.

[0110] Comparative Example 1

[0111] A fluoride-containing denture resin material for preventing dental caries, comprising the following raw material components by weight parts:

[0112] Modified polymethyl methacrylate (the content of hydroxyethyl methacrylate is 5%) 68 parts;

[0113] GA@HBN antibacterial composite 4 parts;

[0114] Nano ZrO2 3 parts;

[0115] 1.1 parts of polyvinyl alcohol emulsifier;

[0116] 2 parts of titanate coupling agent NDZ-2010;

[0117] 0.3 parts of KH-570 silane coupling agent;

[0118] Benzoyl peroxide 0.8 parts;

[0119] 0.1 parts of 2,6-di-tert-butyl-p-cresol.

[0120] The preparation steps of a fluoride-added denture resin material for preventing tooth decay are as follows:

[0121] S1. Weigh the modified polymethyl methacrylate, benzoyl peroxide, and 2,6-di-tert-butyl-p-cresol by weight, add them to a planetary mixer, and stir at 200 r / min for 12 min at 25°C; weigh and add the GA@HBN antibacterial composite material and KH-570 silane coupling agent by weight, and stir at 200 r / min for 3 min; add nano ZrO2 and titanate coupling agent NDZ-201, and stir at 200 r / min for 3 min; reduce the speed to 50 r / min, weigh and add the polyvinyl alcohol emulsifier by weight, and stir for 3 min to obtain the premix;

[0122] S2. Transfer the premix to a three-roll mill with a roller spacing of 50 μm and a roller speed ratio of 1:3:9. Repeat the process 3 times to obtain the premix. Place the premix in a vacuum degassing machine at a vacuum degree of -0.095 MPa and a temperature of 25°C for 15 min to obtain the crude resin material.

[0123] S3. Pour the crude resin material into the resin tank, turn on the DLP light curing printer, select the 405nm light source, and set the light intensity to 15mW / cm². 2 Import the designed model file, set the layer thickness to 50μm, and after printing, place the model along with the water-soluble PVA support into 40℃ warm water and soak for 30 minutes until the support dissolves. Point the infrared thermal imager at the printing area to ensure that the temperature is below 60℃. If the temperature exceeds the limit, stop printing and reduce the light intensity or increase the interlayer cooling time.

[0124] S4. Take 100 mL of anhydrous ethanol, add 0.1 g of perfluorooctyltriethoxysilane, stir for 5 min until dissolved to prepare a fluorosilane solution. Completely immerse the printed part in the fluorosilane solution, let it stand at 25℃ for 30 min, then dry it in a 60℃ oven for 45 min. Place the dried model in a UV curing chamber, set the wavelength to 365 nm and the UV intensity to 10 mW / cm². 2Strength, irradiation 18 min, 50℃ oven for 1h, oven temperature to 80℃ for 2h, natural cooling to room temperature, to get fluoride dental caries prevention denture resin material.

[0125] The difference between the present comparative example and example 1 is that no self-repairing microcapsules are added.

[0126] Comparative example 2

[0127] A fluoride dental caries prevention denture resin material includes the following raw material components by weight fraction:

[0128] Modified polymethyl methacrylate (hydroxyethyl methacrylate content 5%) 68 parts;

[0129] Self-repairing microcapsules 9 parts;

[0130] GA@HBN antibacterial composite 4 parts;

[0131] Polyvinyl alcohol emulsifier 1.1 parts;

[0132] Titanate coupling agent NDZ-201 0.2 parts;

[0133] KH-570 silane coupling agent 0.3 parts;

[0134] Benzoyl peroxide 0.8 parts;

[0135] 2,6-di-tert-butyl-p-cresol 0.1 parts.

[0136] A fluoride dental caries prevention denture resin material preparation steps are as follows:

[0137] S1, modified polymethyl methacrylate, benzoyl peroxide and 2,6-di-tert-butyl-p-cresol are weighed by weight fraction, added to a planetary mixer, stirred at 25℃ at a speed of 200r / min for 12min; GA@HBN antibacterial composite and KH-570 silane coupling agent are weighed by weight fraction and added, stirred at a speed of 200r / min for 3min, titanium coupling agent NDZ-201 is added, stirred at a speed of 200r / min for 3min; the speed is reduced to 50r / min, self-repairing microcapsules and polyvinyl alcohol emulsifier are weighed by weight fraction and added, stirred for 3min, to obtain a premix;

[0138] S2, the premix is transferred to a three-roll mill, the roll spacing is 50μm, the roll speed ratio is 1:3:9, and the cycle is 3 times, to obtain a premix; the premix is placed in a vacuum defoaming machine, the vacuum degree is-0.095MPa, 25℃, and defoaming for 15min, to obtain a crude resin material;

[0139] S3, pour the crude resin material into the resin tank, turn on the DLP photocuring printer, select the 405nm light source, set the light intensity to 15mW / cm 2 , import the designed model file, set the layer thickness to 50pm, after printing, put the model together with the water-soluble PVA support into 40℃ warm water, soak for 30min until the support dissolves, aim the infrared thermal imager at the printing area to ensure the temperature is below 60℃, if the temperature is too high, pause the printing and reduce the light intensity or increase the interlayer cooling time;

[0140] S4, take 100mL anhydrous ethanol, add 0.1g perfluorooctyltriethoxysilane, stir for 5min until dissolved, prepare a fluorosilane solution, immerse the printed piece in the fluorosilane solution, stand at 25℃ for 30min, put it into a 60℃ oven to dry for 45min, put the dried model into a UV curing box, set the wavelength to 365nm, the intensity to 10mW / cm 2 , irradiate for 18min, stand in a 50℃ oven for 1h, raise the oven temperature to 80℃ and stand for 2h, naturally cool to room temperature, obtain the fluoride-containing denture resin material for preventing dental caries.

[0141] The difference between the present example and Example 1 is that no nano-ZrO2 is added.

[0142] Comparative Example 3

[0143] A fluoride-containing denture resin material for preventing dental caries, comprising the following raw material components by weight fraction:

[0144] Polymethyl methacrylate 68 parts;

[0145] Self-repairing microcapsules 9 parts;

[0146] GA@HBN antibacterial composite 4 parts;

[0147] Nano-ZrO2 3 parts;

[0148] Polyvinyl alcohol emulsifier 1.1 parts;

[0149] Titanate coupling agent NDZ-201 0.2 parts;

[0150] KH-570 silane coupling agent 0.3 parts;

[0151] Benzoyl peroxide 0.8 parts;

[0152] 2,6-di-tert-butyl-p-cresol 0.1 part.

[0153] The preparation steps of a fluoride-containing denture resin material for preventing dental caries are as follows:

[0154] S1, weigh the polymethyl methacrylate, benzoyl peroxide and 2,6-di-tert-butyl-p-cresol by weight parts, add them into a planetary mixer, stir at 25℃ with a speed of 200r / min for 12min; weigh and add the GA@HBN antibacterial composite and KH-570 silane coupling agent by weight parts, stir at a speed of 200r / min for 3min, add nano ZrO2 and titanium ester coupling agent NDZ-201, stir at a speed of 200r / min for 3min; reduce the speed to 50r / min, weigh and add the self-repairing microcapsules and polyvinyl alcohol emulsifier by weight parts, stir for 3min to obtain a premix;

[0155] S2, transfer the premix to a three-roll grinder with a roll spacing of 50μm, a roll speed ratio of 1:3:9, and circulate for 3 times to obtain a premix; place the premix in a vacuum defoaming machine with a vacuum degree of-0.095MPa at 25℃ and defoam for 15min to obtain a crude resin material;

[0156] S3, pour the crude resin material into a resin tank, turn on the DLP light curing printer, select a 405nm light source, set the light intensity to 15mW / cm 2 , import the designed model file, set the layer thickness to 50μm, after printing, place the model together with the water-soluble PVA support into 40℃ warm water, soak for 30min until the support dissolves, aim the infrared thermal imager at the printing area to ensure that the temperature is below 60℃, if the temperature is too high, pause the printing and reduce the light intensity or increase the interlayer cooling time;

[0157] S4, take 100mL of anhydrous ethanol, add 0.1g of perfluorooctyltriethoxysilane, stir for 5min until dissolved, configure a fluorosilane solution, completely immerse the printed piece in the fluorosilane solution, stand for 30min at 25℃, place it in a 60℃ oven to dry for 45min, place the dried model in a UV curing box, set the wavelength to 365nm, the intensity to 10mW / cm 2 , irradiate for 18min, stand in a 50℃ oven for 1h, raise the oven temperature to 80℃ and stand for 2h, naturally cool to room temperature to obtain the fluoride-added denture resin material for preventing dental caries.

[0158] The difference between the present example and Example 1 is that the modified polymethyl methacrylate is not added, but the unmodified polymethyl methacrylate is added as the main resin.

[0159] Comparative Example 4

[0160] A fluoride-added denture resin material for preventing dental caries, comprising the following raw material components by weight parts:

[0161] Modified polymethyl methacrylate (content of hydroxyethyl methacrylate is 5%) 68 parts;

[0162] Self-repairing microcapsules 9 parts;

[0163] GA@HBN antibacterial composite 4 parts;

[0164] Nano ZrO2 23 parts;

[0165] Polyvinyl alcohol emulsifier 1.1 parts;

[0166] Titanate coupling agent NDZ-201 0.2 parts;

[0167] KH-570 silane coupling agent 0.3 parts;

[0168] Benzoyl peroxide 0.8 parts;

[0169] 2,6-di-tert-butyl-p-cresol 0.1 parts.

[0170] The preparation steps of a fluorine-added denture resin material for preventing dental caries are as follows:

[0171] S1, weigh the modified polymethyl methacrylate, benzoyl peroxide and 2,6-di-tert-butyl-p-cresol by parts, add them into a planetary mixer, stir at 25℃ and 200r / min for 12min; weigh and add GA@HBN antibacterial composite and KH-570 silane coupling agent by parts, stir at 200r / min for 3min, add nano ZrO2 and titanate coupling agent NDZ-201, stir at 200r / min for 3min; reduce the speed to 50r / min, weigh and add self-repairing microcapsules and polyvinyl alcohol emulsifier by parts, stir for 3min, and get a premix;

[0172] S2, transfer the premix to a three-roll grinder, with a roll spacing of 50μm, a roll speed ratio of 1:3:9, and a cycle of 3 times, to get a premix; put the premix into a vacuum defoaming machine, with a vacuum degree of-0.095MPa, 25℃, and defoaming for 15min, to get a crude resin material;

[0173] S3, pour the crude resin material into a resin tank, turn on the DLP photocuring printer, select a 405nm light source, set the light intensity to 15mW / cm 2 , import the designed model file, set the layer thickness to 50μm, after printing, put the model together with water-soluble PVA support into 40℃ warm water, soak for 30min until the support dissolves, aim the infrared thermal imager at the printing area to ensure the temperature is lower than 60℃, if the temperature is too high, pause the printing and reduce the light intensity or increase the interlayer cooling time;

[0174] S4, put the printed part into a UV curing box, set the wavelength to 365nm and the light intensity to 10mW / cm 2Strength, irradiation 18 min, 1 h in an oven at 50℃, oven temperature to 80℃ for 2 h, natural cooling to room temperature, to obtain the denture resin material for preventing dental caries.

[0175] The difference between the present comparative example and Example 1 is that the printing piece prepared in step S3 is not subjected to the surface fluorination treatment step of original step S4.

[0176] Comparative Example 5

[0177] A fluorine-added denture resin material for preventing dental caries comprises the following raw material components by weight fraction:

[0178] Modified polymethyl methacrylate (hydroxyethyl methacrylate content 5%) 68 parts;

[0179] Self-repairing microcapsule 9 parts;

[0180] Nano ZrO2 23 parts;

[0181] Polyvinyl alcohol emulsifier 1.1 parts;

[0182] Titanate coupling agent NDZ-201 0.2 parts;

[0183] KH-570 silane coupling agent 0.3 parts;

[0184] Benzoyl peroxide 0.8 parts;

[0185] 2,6-di-tert-butyl-p-cresol 0.1 parts.

[0186] A fluorine-added denture resin material for preventing dental caries is prepared by the following steps:

[0187] S1, modified polymethyl methacrylate, benzoyl peroxide and 2,6-di-tert-butyl-p-cresol are weighed by weight fraction, added to a planetary mixer, stirred at 25℃ at a speed of 200 r / min for 12 min; KH-570 silane coupling agent is weighed and added by weight fraction, stirred at a speed of 200 r / min for 3 min, nano ZrO2 and titanate coupling agent NDZ-201 are added, stirred at a speed of 200 r / min for 3 min; the speed is reduced to 50 r / min, self-repairing microcapsule and polyvinyl alcohol emulsifier are weighed and added by weight fraction, stirred for 3 min, to obtain a premix;

[0188] S2, the premix is transferred to a three-roll mill, the roll spacing is 50 μm, the roll speed ratio is 1:3:9, and the cycle is 3 times, to obtain a premix; the premix is placed in a vacuum defoaming machine, the vacuum degree is -0.095 MPa, 25℃, and defoaming is carried out for 15 min, to obtain a crude resin material;

[0189] S3, pour the crude resin material into the resin tank, turn on the DLP light curing printer, select the 405 nm light source, set the light intensity to 15 mW / cm 2 , import the designed model file, set the layer thickness to 50 μm, after printing, put the model together with the water-soluble PVA support into 40℃ warm water, soak for 30 min until the support dissolves, aim the infrared thermal imager at the printing area to ensure that the temperature is below 60℃, if the temperature is too high, pause the printing and reduce the light intensity or increase the interlayer cooling time;

[0190] S4, take 100 mL of anhydrous ethanol, add 0.1 g of perfluorooctyltriethoxysilane, stir for 5 min until dissolved, prepare a fluorosilane solution, immerse the printed piece in the fluorosilane solution, stand at 25℃ for 30 min, put it into a 60℃ oven to dry for 45 min, put the dried model into a UV curing box, set the wavelength to 365 nm, the intensity to 10 mW / cm 2 , irradiate for 18 min, stand in a 50℃ oven for 1 h, raise the oven temperature to 80℃ and stand for 2 h, naturally cool to room temperature, obtain the fluoride-added denture resin material for preventing dental caries.

[0191] The difference between this comparative example and Example 1 is that no GA@HBN antibacterial composite material is added.

[0192] The source of the material is shown in Table 1.

[0193] Table 1

[0194]

[0195]

[0196] Test:

[0197] I. Mechanical properties

[0198] 1. Vickers hardness: ASTM D785 Plastic Rockwell Hardness Test

[0199] 2. Bending strength and bending modulus of elasticity: ISO 20795-1 Denture Base Polymers (Specialized for Dental Resins)

[0200] 3. Impact strength: ISO 179-1 Plastic Charpy Impact Test

[0201] 4. Wear rate: ASTM D4060 Plastic Wear Resistance Test (Taber Abrasion Method)

[0202] Wear rate = mass loss / (density x sliding distance) x 100%

[0203] The test results are shown in Table 2.

[0204] II. Antibacterial properties

[0205] 1. Fungal inhibition rate (C. albicans): JIS Z 2801 Test method for antibacterial property of plastic

[0206] 2. Bacterial inhibition rate (S. mutans, S. aureus, E. coli): ISO 22196 Evaluation of antibacterial property of plastics

[0207] The test results are shown in Table 2.

[0208] III. Color stability

[0209] Color value: ISO / TR 28642 Guide to color stability of dental materials

[0210] The test results are shown in Table 2.

[0211] Table 2

[0212]

[0213]

[0214] From Table 2, it can be seen that the fluoride-containing denture resin materials prepared in Examples 1-3 all have excellent mechanical properties, antibacterial properties and color stability.

[0215] Although embodiments of the present application have been shown and described, it is to be understood that various modifications, substitutions, replacements and changes can be made to these embodiments without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.

[0216] In the description of the specification, the description of the terms "one embodiment", "an example", "a specific example" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Also, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0217] The above is only an example and description of the present application, and those skilled in the art can make various modifications or supplements or use similar ways to replace the described specific embodiments, as long as they do not deviate from the invention or exceed the scope defined by the present claims, and should belong to the protection scope of the present application.

Claims

1. A method for preparing a fluoride-containing anti-cariogenic denture resin material, characterized by: Specifically comprising the following steps: S1, in parts by weight, 59.5-76.5 parts of modified polymethyl methacrylate, 0.7-0.9 parts of initiator and 0.08-0.12 parts of antioxidant are weighed and added to a planetary mixer, stirred at 25°C at a speed of 200r / min for 10-15min; 3.5-4.5 parts of GA@HBN antibacterial composite and 0.25-0.35 parts of compatibilizer are weighed and added, stirred at a speed of 200r / min for 1-3min, 2.4-3.6 parts of nano ZrO2 and 0.16-0.24 parts of dispersant are added, stirred at a speed of 200r / min for 1-3min; the speed is reduced to 50r / min, 8-10 parts of self-repairing microcapsule and 1-1.2 parts of stabilizer are weighed and added, stirred for 3-5min, and a premix is obtained; S2, the premix is transferred to a three-roll mill, the roll spacing is 50μm, the roll speed ratio is 1:3:9, and the cycle is 3 times, and a premix is obtained; the premix is placed in a vacuum defoaming machine, the vacuum degree is-0.095MPa, 25°C, and defoaming is carried out for 15min, and a crude resin material is obtained; S3, pour the crude resin material into the resin tank, turn on the DLP light curing printer, select the 405nm light source, set the light intensity to 15mW / cm², import the designed model file, and set the layer thickness to 50μm; after printing, the model is placed together with the water-soluble PVA support in 40°C warm water, and soaked for 30min until the support is dissolved; S4, configure a fluorosilane solution, immerse the printed part in the fluorosilane solution, stand for 30min at 25°C, and put it into a 60°C oven for drying for 30-60min; put the dried model into an ultraviolet curing box, set the wavelength to 365nm, the intensity to 8-12mW / cm², and irradiate for 15-20min; stand in a 50°C oven for 40-80min, raise the temperature of the oven to 80°C and stand for 90-150min, and naturally cool to room temperature to obtain a denture resin material for preventing dental caries; The modified polymethyl methacrylate is a PMMA-HEMA copolymer subjected to toughening copolymerization modification treatment with hydroxyethyl methacrylate, wherein the content of hydroxyethyl methacrylate is 4-6%; The preparation method of the self-repairing microcapsule is as follows: In the ethylene maleic anhydride aqueous solution, urea, ammonium chloride and deionized water are added, the pH is adjusted to 2.4-3.5, and stirring is carried out at a speed of 150r / min for 30min; the core material and the polymerization inhibitor are added dropwise to the above obtained solution, and stirring is carried out at a speed of 400r / min for 15min; the formaldehyde solution is slowly added, the temperature is raised to 55°C at a rate of 10°C / min, and stirring is continuously carried out for 4h; after washing and drying, the self-repairing microcapsule is obtained; The core material is triethylene glycol dimethacrylate with a mass fraction of 99% and N,N-bis(2-hydroxyethyl)-p-toluidine with a mass fraction of 1%. The amount ratio of the ethylene maleic anhydride aqueous solution, urea, ammonium chloride, deionized water, core material, polymerization inhibitor and formaldehyde solution is (20-30) mL:(2-3) g:(0.2-0.3) g:100 mL:(48-72) mL:(25.2-37.8) mg:(4.64-6.96) mL; The preparation steps of the GA@HBN antibacterial composite material are as follows: A1, hexagonal boron nitride powder is added to an ethanol aqueous solution, magnetically stirred at a speed of 200 r / min for 30 min to preliminarily disperse, transferred to an ultrasonic cleaner, ultrasonically treated for 24 h, centrifuged at a speed of 3000 r / min for 30 min, the precipitate is discarded, the supernatant is collected, frozen, and boron nitride is obtained; A2, the boron nitride is dispersed in deionized water to obtain a boron nitride dispersion liquid; A3, gallic acid is dissolved in deionized water to obtain a GA solution, magnetically stirred at a speed of 500 r / min for 10 min, the boron nitride dispersion liquid obtained in step A2 is added, magnetically stirred at a speed of 200 r / min at 80℃ for 24 h, centrifuged at a speed of 5000 r / min for 15 min, the precipitate is collected, freeze-dried, and a GA@HBN antibacterial composite material is obtained; The stabilizer is a polyvinyl alcohol emulsifier; The dispersing agent is titanium acid ester coupling agent NDZ-201; The compatibilizer is KH-570 silane coupling agent; The initiator is benzoyl peroxide; The antioxidant is 2,6-di-tert-butyl-p-cresol.

2. The method for preparing a fluoride-added denture resin material for preventing dental caries according to claim 1, characterized in that: The volume ratio of ethanol to water in the ethanol aqueous solution in step A1 is 1:1, and the amount ratio of the hexagonal boron nitride powder to the ethanol aqueous solution is 1 g:100 mL; the amount ratio of the boron nitride to the deionized water in step A2 is 1 g:100 mL; the amount ratio of the gallic acid to the deionized water in step A3 is 1 g:50 mL, and the volume ratio of the GA solution to the boron nitride dispersion liquid is 14:

3.

3. A method for preparing a fluorine-containing denture resin material for preventing dental caries according to any one of claims 1-2.

3. A fluorine-containing denture resin material for preventing dental caries prepared by the method according to any one of claims 1-2.

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