CN114316135A - Bulk filling dental composite resin with efficient antibacterial property and preparation method thereof - Google Patents
Bulk filling dental composite resin with efficient antibacterial property and preparation method thereof Download PDFInfo
- Publication number
- CN114316135A CN114316135A CN202111668649.7A CN202111668649A CN114316135A CN 114316135 A CN114316135 A CN 114316135A CN 202111668649 A CN202111668649 A CN 202111668649A CN 114316135 A CN114316135 A CN 114316135A
- Authority
- CN
- China
- Prior art keywords
- spherical
- composite resin
- zinc
- dental composite
- nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention provides a bulk filling dental composite resin with efficient antibacterial property, which is formed by curing a composition comprising the following components: polymerizable resin monomers, inorganic fillers, inorganic antibacterial agents and other additives; the inorganic antibacterial agent is a zinc-containing nano-cluster inorganic antibacterial agent. The invention adopts metal nanoparticle sol and zinc-containing nanoparticle sol as raw materials, and obtains the zinc-containing nano cluster inorganic antibacterial agent through a specific sintering process, wherein the structure of the zinc-containing nano cluster inorganic antibacterial agent is a nano cluster structure and is used as a dental material antibacterial agent, so that the antibacterial activity of the composite resin is greatly improved, and the dental composite resin has good antibacterial performance for a long time.
Description
Technical Field
The invention relates to the technical field of dental materials, in particular to a bulk filling dental composite resin with efficient antibacterial property and a preparation method thereof.
Background
Dental caries is a common dental multiple disease and is one of the most common diseases of human beings, and the world health organization combines the dental caries with cancer and cardiovascular diseases as three major prevention and treatment diseases of human beings. The pathogenesis of the dental caries is that organic matters are fermented by cariogenic bacteria in bacterial plaque around teeth to generate acid substances, and inorganic components of tooth tissues are damaged. The dental composite resin is widely applied to clinical dental caries repair due to the characteristics of beautiful color, convenient operation, excellent physicochemical and safety properties and the like.
The large-block filling dental composite resin can fill cavities with the depth of 4mm at one time, has low polymerization shrinkage, simplifies clinical operation, avoids gaps and pollution between resin layers, and has extremely high clinical application value in the aspect of repairing deeper cavities. However, the tooth body repaired by the composite resin has inevitable gaps at the edges of the filling materials, and protein and carbohydrate are easily adsorbed at the gaps to become main places for oral bacteria to gather, so that inorganic components in the tooth body tissue are continuously damaged, and finally secondary caries is caused. Therefore, the function of the dental composite resin for resisting bacteria and preventing caries gradually becomes the main embodiment of the functionalization of dental repair products while reducing polymerization shrinkage and improving mechanical properties. At present, most of bulk filling dental composite resin is remineralized with adjacent hard tooth tissues by adding fluorine-containing inorganic fillers such as ytterbium fluoride, fluorine-containing glass powder and the like, and the demineralization resistance of the hard tissues is improved, so that the occurrence of secondary caries of the hard tooth tissues is inhibited/prevented. Although the fluorine-containing bulk filling dental composite resin can have a certain sterilization effect on cariogenic bacteria by releasing fluorine ions, a large amount of cariogenic bacteria still adhere to the surface of the cured composite resin prosthesis, and the residual bacteria can continuously damage the dental tissues at the edge of the filling material and still have a large risk of secondary caries. Compared with the prior art, the one or more high-efficiency inorganic antibacterial agents are introduced, so that the metal ions are released for a long time, the strong sterilization and antibacterial effects are realized on cariogenic bacteria gathered at the edges of the filler, the harm caused by the cariogenic bacteria can be effectively reduced, the occurrence of secondary caries is avoided, and the oral health of a patient is protected.
For example, patent CN 102688150 a introduces a nano silver inorganic antibacterial agent modified by oleic acid, and mixes the nano silver inorganic antibacterial agent with modified inorganic filler, organic monomer and initiator to prepare dental repair composite resin with good antibacterial performance, and when the silver content of the composite resin is 200ppm (wt%), the antibacterial rate is as high as 100%. However, the pure silver system inorganic antibacterial agent has the problem of easy color change, which affects the appearance, reduces the transparency of the dental composite resin, increases the impermeability of the irradiated light, greatly reduces the curing depth of the resin, and is difficult to meet the curing depth requirement of the bulk filling composite resin. In addition, it has been found that excessive silver causes pigmentation by aggregation in the human body and even causes damage or lesions to tissues such as the oral cavity and the skin, which limits the use of the Ag-containing antibacterial agent.
The zinc system inorganic antibacterial agent has strong inhibiting or killing effects on pathogenic bacteria such as escherichia coli, staphylococcus aureus, salmonella and the like, wherein the nano zinc oxide has the characteristics of high biological activity, good immunoregulation capability, high absorption rate and the like while having low toxicity and good biocompatibility, and shows excellent sterilizing and bacteriostasis effects when the particle size of the particles is reduced to the nano level (20-30 nm). However, the nano-scale zinc oxide has high surface energy, is easy to adhere to each other and gather into loose network chain-shaped secondary particles, has great thickening effect and uneven dispersion, and influences the addition of other inorganic fillers. The submicron zinc oxide has small specific surface area and low antibacterial strength, can improve the antibacterial property of the dental composite resin only by adding excessive zinc system inorganic antibacterial agent, can greatly reduce the mechanical property of the dental composite resin, has poor wear resistance, is easy to fall off from the surface of the resin, and has no long-term antibacterial property.
For example, CN 109453034B adds silane modified ZnO mesomorphic microballoon with the grain size of 800 nm-1 μm into the dental composite resin, when the filling amount of zinc oxide is 20%, the antibacterial rate of the composite resin can reach 99.9%. However, as the adopted ZnO mesomorphic microspheres are submicron particles and the contact and reaction area with bacteria is small, the sterilization and bacteriostasis efficiency is low, and high-content ZnO needs to be added. Although the antibacterial property of the dental composite resin can be improved by adding the submicron or micron zinc system inorganic antibacterial agent excessively, the mechanical property of the dental composite resin can be greatly reduced, and the demand of people cannot be met. Therefore, the current measures cannot simultaneously realize bulk filling and long-term high-efficiency antibacterial performance of the dental composite resin.
In addition, the traditional light-cured dental composite resin material has large refractive index difference between the inorganic filler and the resin matrix, has low transparency, and can only penetrate the material to a limited depth by light required by curing, so that the thickness of each layer of material after curing is generally not more than 3mm, a layered filling technology is usually required when filling deeper cavities, the layered filling is time-consuming, and air bubbles may exist between different resin layers in the filling process, thereby greatly influencing the filling effect.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a bulk filling dental composite resin with high antibacterial property and a preparation method thereof, wherein the prepared composite resin has bulk filling property, and simultaneously has excellent antibacterial property, mechanical property and abrasion resistance.
The invention provides a bulk filling dental composite resin with efficient antibacterial property, which is formed by curing a composition comprising the following components: polymerizable resin monomers, inorganic fillers, inorganic antibacterial agents and other additives;
the inorganic antibacterial agent is a zinc-containing nano-cluster inorganic antibacterial agent.
Preferably, the composition comprises, by mass:
in the present invention, "bulk filling" refers to a dental polymer-based restorative material having a cure depth requirement of not less than 4mm, as tested according to ISO 4049:2009 standard.
In the present invention, the polymerizable resin monomer includes a main monomer and a reactive diluent monomer.
The main monomer is preferably one or more of 3, 4-epoxy cyclohexyl formate (EE), bisphenol A-glycidyl dimethacrylate (Bis-GMA), alicyclic dicarboxylic acid dimethacrylate (DCDMA), ethoxylated bisphenol A dimethacrylate (Bis-EMA), Urethane Dimethacrylate (UDMA), aromatic cluster diisocyanate dimethacrylate (AUDMA), 1, 12-dodecanediol dimethacrylate (DDDMA); more preferred are 3, 4-epoxycyclohexylformate (EE), bisphenol A-glycidyl dimethacrylate (Bis-GMA), ethoxylated bisphenol A dimethacrylate (Bis-EMA), Urethane Dimethacrylate (UDMA) and 1, 12-dodecanediol dimethacrylate (DDDMA). The mass ratio of the 3, 4-epoxycyclohexyl formate (EE), the bisphenol A-glycidyl dimethacrylate (Bis-GMA), the ethoxylated bisphenol A dimethacrylate (Bis-EMA), the Urethane Dimethacrylate (UDMA) and the 1, 12-dodecanediol dimethacrylate (DDDMA) is preferably (6-7): (20-21): (14-16): (15-16): (13-14), more preferably 7.3:20.7:15:15.6: 13.6.
The reactive diluent monomer is preferably one or more of triethylene glycol dimethacrylate (TEGDMA), hydroxyethyl methacrylate (HEMA) and 1, 6-hexanediol diacrylate; more preferred are triethylene glycol dimethacrylate (TEGDMA) and hydroxyethyl methacrylate (HEMA). The mass ratio of the triethylene glycol dimethacrylate (TEGDMA) to the hydroxyethyl methacrylate (HEMA) is preferably (23-24): (3-4); more preferably 23.2: 3.6.
In the present invention, the mass content of the polymerizable resin monomer is preferably 15% to 40%, more preferably 20% to 30%, and still more preferably 20%. Wherein the mass ratio of the main monomer to the reactive diluent monomer is preferably (2-3): 1, more preferably (2 to 2.5): 1, more preferably 2.32: 1.
In the present invention, the inorganic filler includes a structural filler and a nano filler.
The structural filler is preferably spherical structural filler and comprises submicron particles and micron particles, the particle size of the submicron particles is preferably 0.1-1.0 μm, and preferably, the main particle sizes of the submicron particles are respectively distributed in 0.1-0.3 μm and 0.5-0.9 μm, and in some specific embodiments of the invention, the particle size of the submicron particles is 0.2 μm and 0.7 μm; the particle size of the microparticles is preferably 1.0-5.0 microns, and preferably, the main particle size distribution thereof is 2.0-3.0 microns, and in some embodiments of the invention, the particle size of the microparticles is 1.5 microns and 3.0 microns; the mass ratio of the submicron particles to the micron particles is preferably (1-30): 1, more preferably (1 to 10): 1, more preferably (1-3): 1.
the structural filler is preferably one or more of spherical silicon oxide, spherical zirconium oxide, spherical aluminum oxide, spherical tantalum oxide, spherical aluminum silicate, spherical barium aluminum silicate, spherical fluorine-containing glass powder, spherical barium glass powder and spherical strontium glass powder which are treated by a silane coupling agent.
The nano filler is preferably a spherical nano filler, the particle size is preferably 10-100 nm, more preferably 10-50 nm, even more preferably 20-40 nm, and even more preferably 30 nm.
The nano filler is preferably one or more of spherical nano silicon oxide, spherical nano zirconium oxide, spherical nano titanium dioxide, spherical nano aluminum oxide, spherical nano hydroxyapatite, spherical nano ytterbium fluoride, spherical nano yttrium fluoride and spherical nano barium titanate which are treated by a silane coupling agent.
The silane coupling agent is not particularly limited in kind in the present invention, and may be one known to those skilled in the art, and the surface treatment with 3- (methacryloyloxy) propyltrimethoxysilane is preferred in the present invention.
The treatment method of the silane coupling agent is not particularly limited, and can be a silane coupling agent surface treatment method well known to those skilled in the art, preferably, the filler and an ethanol solvent are mixed to prepare filler slurry, meanwhile, the silane coupling agent is mixed with an ethanol water solution, the pH value is adjusted to 3.0-4.0, and a prehydrolysis reaction is carried out under the heating condition until the silane coupling agent is completely hydrolyzed; and mixing the hydrolyzed silane coupling agent solution with the filler slurry, and modifying at 100-150 ℃ for 2-6 h preferably to obtain the silane coupling agent modified filler. Preferably, after modification, the modified product is dried in vacuum at 100-150 ℃ for 10-15 h.
Glacial acetic acid is preferably used for the pH adjustment.
The heating temperature is preferably 100 to 150 ℃, and the time of the prehydrolysis reaction is preferably 30 to 60 min.
The mass ratio of the silane coupling agent, ethanol and water is preferably 2:5: 3.
The amount of the silane coupling agent is preferably 2 to 10% by mass of the filler.
The mass content of the inorganic filler is preferably 60% to 85%, more preferably 70% to 80%.
Wherein the mass ratio of the structural filler to the nano filler is preferably (3-30): 1.
Wherein, the mass content of the structural filler is preferably 60 to 80 percent, and more preferably 70 to 75 percent; the mass content of the nano filler is preferably 0.1-5%; more preferably 0.1% to 3%.
The structural filler and the nano filler are spherical fillers, the polishing performance of the spherical fillers is superior to that of fillers with irregular shapes, and the spherical fillers can well transfer stress with a resin matrix uniformly, reduce the stress concentration of the resin matrix and enhance the strength of the resin. Meanwhile, the grain diameters of the structural filler and the nano filler have the characteristic of wide distribution, and the use amounts are optimized and proportioned, so that the gaps among the fillers are effectively reduced, and the packing density of the fillers is improved.
In the invention, the zinc-containing nanocluster inorganic antibacterial agent is preferably one or more of a silicon dioxide-zinc oxide nanocluster inorganic antibacterial agent, a titanium dioxide-zinc oxide nanocluster inorganic antibacterial agent and an aluminum oxide-zinc oxide nanocluster inorganic antibacterial agent.
In the invention, the zinc-containing nano-cluster inorganic antibacterial agent is prepared by the following method:
s1) mixing the metal nanoparticle sol and the zinc-containing nanoparticle sol to obtain a mixed sol of the metal nanoparticles and the zinc nanoparticles;
the metal nanoparticle sol is selected from one or more of silica sol, titanium dioxide sol and alumina sol;
the zinc-containing nanoparticle sol is selected from zinc oxide sol;
s2) heating the mixed sol to 200-800 ℃, and then grinding to obtain the zinc-containing nano-cluster inorganic antibacterial agent.
Preferably, in the metal nanoparticle sol, the average particle size of the metal nanoparticles is 10-100 nm; more preferably 10 to 30nm, and still more preferably 30 nm.
Preferably, in the zinc-containing nanoparticle sol, the average particle size of the zinc-containing nanoparticles is 5-100 nm; more preferably 10 to 30 nm.
The particle size of the zinc-containing nano-cluster inorganic antibacterial agent is preferably 0.01-10 mu m, and the color and transparency of the dental composite resin are not affected.
The mass content of the zinc-containing nano-cluster inorganic antibacterial agent is preferably 0.1-10%, more preferably 3-7%, and even more preferably 3-5%.
In the present invention, preferably, the metal nanoparticle sol and the zinc-containing nanoparticle sol are both particles treated with a silane coupling agent, and the silane coupling agent and the treatment method are the same as above and are not described herein again.
The zinc is a trace element necessary for human body, the content of the zinc is second to that of iron, and the trace element of zinc is harmless to human body and is beneficial to the growth of human body, so that the zinc system inorganic antibacterial agent has good biocompatibility. In addition, the zinc system inorganic antibacterial agent is also beneficial to overcoming the problem of easy color change of the silver system inorganic antibacterial agent, does not influence the transparency of the dental composite resin, and has little influence on the curing depth of the dental composite resin.
The zinc-containing nano-cluster particles can be abraded and shed to release the nano-zinc oxide antibacterial agent in the polishing and abrasion processes, and have high-efficiency antibacterial property.
The antibacterial mechanism of the bulk filling antibacterial dental composite resin is as follows:
the dental composite resin restoration body introduced with the zinc-containing nano-cluster inorganic antibacterial agent releases nano zinc oxide particles in the oral cavity of a human body through abrasion or dissolution. The nano zinc oxide can continuously release Zn in saliva2+Ions, Zn2+Ions with positive charge when there is a trace of Zn2+When the ions contact with the microbes gathered at the edge of the filler, the ions are coulometrically attracted with the microbial cell membrane with negative charges to firmly combine the microbes, and Zn2+The ions penetrate through cell membranes to enter bacteria and react with sulfhydryl groups, amino groups and the like on proteins in the bacteria. The active center of the cell synthetase consists of functional groups containing sulfhydryl, amino, hydroxyl and the like, and Zn2+After ion binding, the structure of the active center of the protein is destroyed, resulting in the death of the microorganism or the loss of the ability to divide and proliferate. After destruction, Zn2+Ions are dissociated from the bacteria, and the sterilization process is repeated. Therefore, the bulk filling dental composite resin provided by the invention can release Zn for a long time2+The ions have strong sterilization and antibacterial effects on cariogenic bacteria gathered at the edges of the filler, thereby effectively avoiding secondary caries and protecting the oral health of patients.
Preferably, the other additives include one or more of pigments, photoinitiators, age resistors, inhibitors, dispersants, rheology modifiers, and the like.
The kind of the other additives is not particularly limited in the present invention, and may be any suitable additives known to those skilled in the art, and the pigment is preferably selected from yellow iron oxide, red iron oxide, black iron oxide, titanium dioxide, etc.; the photoinitiator is selected from one or more of camphorquinone, ethyl p-N, N-dimethylaminobenzoate and TPO; the anti-aging agent is selected from 2-hydroxy-4-methoxybenzophenone, butylated hydroxytoluene and the like; the polymerization inhibitor is selected from 4-methoxyphenol; the rheology modifier is selected from fumed silica.
Preferably, the polymerizable resin monomer and the inorganic filler have similar refractive indexes, both of which are between 1.40 and 1.60, wherein the refractive index of the inorganic filler and the polymerizable resin monomer mixture before curing is different by at most 0.08 and after curing is different by at most 0.12 from that of the dental composite resin.
According to the invention, the polymerizable resin monomer and the inorganic filler are preferably selected to have similar refractive indexes by the types and the dosage, so that the dental composite resin has bulk filling characteristics, excellent mechanical properties and wear resistance. The dental composite resin is in a semitransparent paste or paste state in an uncured state, the volume shrinkage of the cured composite resin is lower than 2.3%, the curing depth is greater than 4mm, the dental composite resin is in a semitransparent state, and the dental composite resin has good long-term antibacterial performance. It produces low shrinkage stress and can increase the curing depth in the polymerization process, can effectively shorten the time of repair treatment when filling deeper cavity, brings better treatment effect for patients.
The invention provides a preparation method of the bulk filling dental composite resin, which comprises the following steps:
s1) mixing one or more polymerizable resin monomers to obtain a resin matrix;
s2) mixing the resin matrix with other additives under the condition of keeping out of the sun to obtain a resin matrix composition;
s3) dispersing the inorganic antibacterial agent in the resin matrix composition, mixing uniformly, adding the inorganic filler, mixing uniformly, and curing under the light curing condition to obtain the bulk filling dental composite resin.
Compared with the prior art, the invention provides a bulk filling dental composite resin with efficient antibacterial property, which is formed by curing a composition comprising the following components: polymerizable resin monomers, inorganic fillers, inorganic antibacterial agents and other additives; the inorganic antibacterial agent is a zinc-containing nano-cluster inorganic antibacterial agent. The invention adopts metal nanoparticle sol and zinc-containing nanoparticle sol as raw materials, and obtains the zinc-containing nano cluster inorganic antibacterial agent through a specific sintering process, wherein the structure of the zinc-containing nano cluster inorganic antibacterial agent is a nano cluster structure and is used as a dental material antibacterial agent, so that the antibacterial activity of the composite resin is greatly improved, and the dental composite resin has good antibacterial performance for a long time.
Detailed Description
In order to further illustrate the present invention, the following examples are provided to describe the bulk filling dental composite resin with high antibacterial property and the preparation method thereof.
In the following examples, abbreviations for the respective materials are shown in Table 1:
abbreviation of materials used in Table 1 examples
And (3) testing the curing depth: according to ISO 4049:2009 test standard, the sample is poured into a metal mold with a diameter of 4mm and a height of 10mm, and irradiated from one side by a visible light curing lamp for 40 seconds. Immediately after the irradiation, the specimen was removed from the mold and the uncured material was removed with a plastic spatula. The height of the cured material cylinder was measured to. + -. 0.1mm using a micrometer, and the measured value was divided by 2, and this value was recorded as the depth of cure.
Flexural strength test: according to the ISO 4049:2009 test standard, a sample is injected into a metal mold with the thickness of 2mm multiplied by 25mm to manufacture a test piece, and the surface and the bottom surface of the test piece are respectively covered by polyester films to prevent matrix from flowing out and prevent an anaerobic layer from existing. Irradiating a curing test piece by a visible light curing lamp, overlapping and irradiating 5 points from left to right, and irradiating each point for 20 seconds to ensure full curing; the test pieces were then stored in distilled water at 37 ℃ for 24 hours in the dark. And (3) carrying out three-point bending strength and elastic modulus test on the test piece by adopting a universal testing machine, loading the test piece at a loading speed of 0.75mm/min, and recording the maximum load and the slope applied when the test piece reaches a breaking point until the test piece breaks. And finally, calculating according to an ISO 4049:2009 test standard formula to obtain the flexural strength and the elastic modulus.
Surface hardness test: the sample was placed in a metal mold having a diameter of 6mm and a height of 2mm to prepare a circular test piece, and the circular test piece was irradiated with visible light curing light for 20 seconds. The test pieces were stored in distilled water at 37 ℃ for 24 hours in the dark. And (3) testing the surface hardness of the experimental material by using a Vickers hardness tester, wherein the loading force is 980mN, the loading lasts for 10 seconds, directly recording the digital display hardness value, testing for 3 times, and taking the average value of the digital display hardness value.
Volume shrinkage test: according to the GB/T9937 standard, the volume shrinkage of the dental composite resin sample is analyzed by adopting a Proto-tech oral cavity material polymerization stress measuring instrument in the United states.
And (3) testing antibacterial performance: according to the standard of ASTM E2180-2007(2012), the antibacterial rate of the dental composite resin on streptococcus mutans, actinomycetes and lactobacillus is quantitatively analyzed.
Examples 1 to 5
1. In examples 1 to 5, the preparation method of the silica-zinc oxide nanocluster inorganic antibacterial agent is as follows:
(1) providing a silica sol comprising silica nanoparticles having an average particle size of 30 nm;
(2) providing a zinc oxide sol comprising zinc oxide nanoparticles having an average particle size of 10-30 nm;
(3) combining the silica sol and the zinc oxide sol to form a mixture of silica nanoparticles and zinc oxide nanoparticles;
(4) the mixture was heated to 800 ℃ for 2 hours, and then the heated mixture was ground to form a silica-zinc oxide nanocluster inorganic antibacterial agent) (particle size 1-5 μm).
2. In examples 1-5, all of the structured fillers, nanofillers and pigments were obtained by the following silane coupling agent treatment process, unless otherwise specified:
(1) weighing a certain mass of filler, adding the filler into an absolute ethyl alcohol solution to prepare filler slurry, and then carrying out ultrasonic treatment for 10-30 min;
(2) preparing an alcohol-water solution from anhydrous ethanol and water according to a certain proportion, adding glacial acetic acid to adjust the pH of the solution to 3.0-4.0, then adding a silane coupling agent, wherein the mass ratio of the ethanol to the water to the silane coupling agent is 5:3:2, and carrying out magnetic stirring for 30-60min under the heating condition of 100 plus materials and 150 ℃ to carry out prehydrolysis reaction until the silane coupling agent is completely hydrolyzed, wherein the amount of the silane coupling agent is 2-10% of the mass content of the filler;
(3) dropwise adding the hydrolyzed silane solution into the filler slurry under stirring, raising the heating temperature to 100-150 ℃, magnetically stirring for 2-6 hours, and then vacuum-drying at 100-150 ℃ for 10-15 hours.
3. The preparation process of the composite resin comprises the following steps:
firstly, one or more polymerizable resin monomers are mixed with each other according to a certain mass ratio to prepare a resin matrix. And then, under the condition of keeping out of the sun and under mechanical stirring, sequentially adding a photoinitiator, an anti-aging agent, a polymerization inhibitor, a dispersing agent and the like in a certain ratio, and fully stirring and mixing to obtain the resin matrix composition. Then, silica-zinc oxide nanocluster inorganic antibacterial agent (nSiO)2-ZnO) in a resin matrix composition, and thoroughly mixing. Finally, grinding and mixing the rheological modifier, the pigment, the structural filler and the nano filler with the resin matrix composition uniformly, and obtaining the bulk filled antibacterial dental composite resin under the irradiation of photocuring light. All parts and percentages are by weight in all examples unless otherwise indicated.
The resin matrix composition components of examples 1-5 are shown in Table 2:
TABLE 2 resin matrix composition Components and amounts in examples 1-5
Examples 1-5 the components and amounts are shown in table 3:
table 3 examples 1-5 amounts of each component
The HEL-40C functions as a solubilizing agent to facilitate mixing of the resin monomer with the filler.
The test results for examples 1-5 are shown in Table 4:
TABLE 4
The above embodiments show that the dental composite resin provided by the invention has bulk filling characteristics, and the curing depth exceeds 4mm, so that the definition requirement of bulk filling resin is met. Compared with the example 1 without adding the silica-zinc oxide nano-cluster inorganic antibacterial agent, other examples with the silica-zinc oxide nano-cluster inorganic antibacterial agent all show good antibacterial performance on streptococcus mutans, lactobacillus and escherichia coli, and when the content of the added silica-zinc oxide nano-cluster inorganic antibacterial agent is 3%, the antibacterial rate of the composite resin in the example 3 on cariogenic bacteria exceeds 96%, which shows that the silica-zinc oxide nano-cluster inorganic antibacterial agent has high antibacterial performance. After being soaked in artificial saliva for half a year, the examples show better antibacterial performance on streptococcus mutans, lactobacillus and escherichia coli, and the antibacterial rate of the examples exceeds 50%, wherein the antibacterial rate of the example 5 exceeds 80%. In addition, examples 3 and 4 show that by adopting the inorganic filler with wide particle size distribution, the use amount of the filler is optimized and proportioned, so that the gaps among the fillers can be effectively reduced, the packing density of the filler is improved, the mechanical properties such as flexural strength, elastic modulus, Vickers hardness and the like of the composite resin can be obviously improved, and the volume shrinkage rate of the composite resin can be reduced.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. A bulk-filled dental composite resin with efficient antibacterial properties is prepared by curing a composition comprising the following components: polymerizable resin monomers, inorganic fillers, inorganic antibacterial agents and other additives;
the inorganic antibacterial agent is a zinc-containing nanocluster inorganic antibacterial agent.
2. The bulk-filled dental composite resin according to claim 1, wherein the composition comprises, in mass content:
3. the bulk-filled dental composite resin according to claim 1, wherein the zinc-containing nanocluster inorganic antibacterial agent is prepared according to the following method:
s1) mixing the metal nanoparticle sol and the zinc-containing nanoparticle sol to obtain a mixed sol of the metal nanoparticles and the zinc nanoparticles;
the metal nanoparticle sol is selected from one or more of silica sol, titanium dioxide sol and alumina sol;
the zinc-containing nanoparticle sol is selected from zinc oxide sol;
s2) heating the mixed sol to 200-800 ℃, and then grinding to obtain the zinc-containing nano-cluster inorganic antibacterial agent.
4. The bulk-filled dental composite resin according to claim 3, wherein the metal nanoparticle sol has an average particle diameter of metal nanoparticles of 10 to 100 nm;
in the zinc-containing nanoparticle sol, the average particle size of zinc-containing nanoparticles is 5-100 nm;
the particle size of the zinc-containing nano-cluster inorganic antibacterial agent is 0.01-10 mu m.
5. The bulk-filled dental composite resin of claim 1, wherein the polymerizable resin monomers comprise a main monomer and a reactive diluent monomer;
the main monomer is selected from one or more of 3, 4-epoxy cyclohexyl formate, bisphenol A-glycidyl dimethacrylate, alicyclic dicarboxylic acid dimethacrylate, ethoxylated bisphenol A dimethacrylate, urethane dimethacrylate, aromatic cluster dimethacrylate diisocyanate and 1, 12-dodecanediol dimethacrylate;
the reactive diluent monomer is selected from one or more of triethylene glycol dimethacrylate, hydroxyethyl methacrylate and 1, 6-hexanediol diacrylate.
6. The bulk-filled dental composite resin according to claim 1, wherein the inorganic filler comprises a structural filler and a nanofiller;
the structural filler is a spherical structural filler and comprises submicron particles and micron particles, the particle size of the submicron particles is 0.1-1.0 micron, and the particle size of the micron particles is 1.0-5.0 micron; the mass ratio of the submicron particles to the micron particles is (1-30): 1;
the nano filler is spherical and has a particle size of 10-100 nm.
7. The bulk-filled dental composite resin according to claim 6, wherein the structural filler is one or more of spherical silica, spherical zirconia, spherical alumina, spherical tantalum oxide, spherical aluminum silicate, spherical barium aluminum silicate, spherical fluorine-containing glass powder, spherical barium glass powder, and spherical strontium glass powder treated with a silane coupling agent;
the nano filler is one or more of spherical nano silicon oxide, spherical nano zirconium oxide, spherical nano titanium dioxide, spherical nano aluminum oxide, spherical nano hydroxyapatite, spherical nano ytterbium fluoride, spherical nano yttrium fluoride and spherical nano barium titanate which are treated by a silane coupling agent.
8. The bulk-filled dental composite resin according to claim 1, wherein the other additives include one or more of pigments, photoinitiators, anti-aging agents, inhibitors, dispersants, rheology modifiers.
9. The bulk-filled dental composite resin according to claim 1, wherein the cured composite resin has a volume shrinkage of less than 2.3% and a depth of cure of greater than 4 mm.
10. The method for preparing a bulk-filled dental composite resin according to any one of claims 1 to 9, comprising the steps of:
s1) mixing one or more polymerizable resin monomers to obtain a resin matrix;
s2) mixing the resin matrix with other additives under the condition of keeping out of the sun to obtain a resin matrix composition;
s3) dispersing the inorganic antibacterial agent in the resin matrix composition, mixing uniformly, adding the inorganic filler, mixing uniformly, and curing under the light curing condition to obtain the bulk filling dental composite resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111668649.7A CN114316135A (en) | 2021-12-30 | 2021-12-30 | Bulk filling dental composite resin with efficient antibacterial property and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111668649.7A CN114316135A (en) | 2021-12-30 | 2021-12-30 | Bulk filling dental composite resin with efficient antibacterial property and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114316135A true CN114316135A (en) | 2022-04-12 |
Family
ID=81021869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111668649.7A Pending CN114316135A (en) | 2021-12-30 | 2021-12-30 | Bulk filling dental composite resin with efficient antibacterial property and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114316135A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115487076A (en) * | 2022-09-16 | 2022-12-20 | 桂林凯文彼德科技有限公司 | Antibacterial nanocluster filler for dental composite resin, preparation method of antibacterial nanocluster filler and dental composite resin |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1245678A (en) * | 1998-06-09 | 2000-03-01 | 科尔公司 | Tooth-repairing composition |
| CN102224106A (en) * | 2008-10-15 | 2011-10-19 | 3M创新有限公司 | Fillers and composite materials with zirconia and silica nanoparticles |
| CN102793627A (en) * | 2011-05-27 | 2012-11-28 | 科尔公司 | Dental restorative material |
| CN108601710A (en) * | 2016-02-05 | 2018-09-28 | 3M创新有限公司 | Including providing the dental composition of the nano-particle of the refringence between polymerizing resin and filler |
| CN109199873A (en) * | 2017-07-06 | 2019-01-15 | 北京化工大学 | A kind of inorganic nano-particle cluster body and preparation method thereof for dental repair resin |
| CN109481317A (en) * | 2017-09-11 | 2019-03-19 | 北京化工大学 | A kind of gear division reparation nanocomposite and preparation method thereof |
-
2021
- 2021-12-30 CN CN202111668649.7A patent/CN114316135A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1245678A (en) * | 1998-06-09 | 2000-03-01 | 科尔公司 | Tooth-repairing composition |
| CN102224106A (en) * | 2008-10-15 | 2011-10-19 | 3M创新有限公司 | Fillers and composite materials with zirconia and silica nanoparticles |
| CN102793627A (en) * | 2011-05-27 | 2012-11-28 | 科尔公司 | Dental restorative material |
| CN108601710A (en) * | 2016-02-05 | 2018-09-28 | 3M创新有限公司 | Including providing the dental composition of the nano-particle of the refringence between polymerizing resin and filler |
| CN109199873A (en) * | 2017-07-06 | 2019-01-15 | 北京化工大学 | A kind of inorganic nano-particle cluster body and preparation method thereof for dental repair resin |
| CN109481317A (en) * | 2017-09-11 | 2019-03-19 | 北京化工大学 | A kind of gear division reparation nanocomposite and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| HENRYA.RODRÍGUEZ等: ""Development of mechanical properties in dental resin composite: Efect of fller size and fller aggregation state"", 《MATERIALS SCIENCE & ENGINEERING C》 * |
| RUILI WANG等: ""Wear behavior of light-cured resin composites with bimodal silica nanostructures as fillers"", 《MATERIALS SCIENCE AND ENGINEERING C》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115487076A (en) * | 2022-09-16 | 2022-12-20 | 桂林凯文彼德科技有限公司 | Antibacterial nanocluster filler for dental composite resin, preparation method of antibacterial nanocluster filler and dental composite resin |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Development of a multifunctional adhesive system for prevention of root caries and secondary caries | |
| Melo et al. | Novel dental adhesives containing nanoparticles of silver and amorphous calcium phosphate | |
| EP2881077B1 (en) | Method for manufacturing dental mill blank | |
| JP5661040B2 (en) | Filler containing zirconia and silica nanoparticles, and composite material | |
| Melo et al. | Novel dental adhesive containing antibacterial agents and calcium phosphate nanoparticles | |
| Hojati et al. | Antibacterial, physical and mechanical properties of flowable resin composites containing zinc oxide nanoparticles | |
| EP2583660B1 (en) | Dental restorative composite | |
| EP2724706B1 (en) | Dental restorative material | |
| EP2571479B1 (en) | Dental compositions | |
| Abdulsamee et al. | Zirconomer and Zirconomer Improved (White Amalgams): Restorative Materi-als for the Future. Review | |
| CN109453034B (en) | Antibacterial dental repair composite resin and preparation and application thereof | |
| BR112012015607A2 (en) | DENTAL COMPOSITIONS, LAMINATION BLOCKS AND METHODS | |
| WO2018070544A1 (en) | Dental composition and dental-cutting processing composite resin material using said dental composition | |
| JP4895443B2 (en) | Dental curable composition | |
| Choe et al. | Investigating the mechanophysical and biological characteristics of therapeutic dental cement incorporating copper doped bioglass nanoparticles | |
| CN114316135A (en) | Bulk filling dental composite resin with efficient antibacterial property and preparation method thereof | |
| De Souza | Nanoparticles in restorative materials | |
| Albeshir et al. | Minimally-invasive dentistry via dual-function novel bioactive low-shrinkage-stress flowable nanocomposites | |
| KR100739935B1 (en) | Composition for photo-polymerized dental restorative nanocomposite material | |
| CN108143634B (en) | Dental root surface protection material composition | |
| Abdallah et al. | Does modification of amalgomer with propolis alter its physicomechanical properties? an in vitro study | |
| EP1940342B1 (en) | Dental sealant compositions containing nanometer-sized silica | |
| JP4271800B2 (en) | Dental multifunctional filler | |
| JP7061826B2 (en) | Dental mill blank | |
| CN112315815B (en) | Preparation method and application of bioactive material containing nano calcium fluoride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |