CN109730935B - High-strength dental composite resin and preparation method thereof - Google Patents
High-strength dental composite resin and preparation method thereof Download PDFInfo
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- CN109730935B CN109730935B CN201910044740.8A CN201910044740A CN109730935B CN 109730935 B CN109730935 B CN 109730935B CN 201910044740 A CN201910044740 A CN 201910044740A CN 109730935 B CN109730935 B CN 109730935B
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Abstract
The invention relates to a high-strength dental composite resin and a preparation method thereof. The preparation method comprises the following steps: premixing spherical mesoporous filler, organic monomer and photoinitiator, putting the mixture into a three-roll grinder for further mixing, adding spherical filler, and performing vacuum negative pressure treatment to obtain uncured composite resin paste; finally, the dental composite resin is obtained through visible light curing. The dental composite resin provided by the invention is simple and convenient in preparation method, excellent in mechanical property and good in application prospect.
Description
Technical Field
The invention belongs to the field of dental restoration materials, and particularly relates to a high-strength dental composite resin and a preparation method thereof.
Background
Since 1962 R.L.Bowen synthesized a famous bisphenol A-glycidyl methacrylate (Bis-GMA), resin-based dental composite resin became an important material for treating caries and tooth defects by ascending due to the characteristics of beautiful color, convenient operation, excellent physicochemical and biological properties, and the like. The resin mainly comprises organic monomers, silanized inorganic filler and photoinitiator, wherein the inorganic filler can be wrapped by the organic monomers distributed in a continuous phase, and a polymer network structure is formed in a free radical polymerization reaction. Despite numerous advances made by researchers in optimizing organic monomer structures, inorganic filler compositions, repairing fractures remains the leading cause of failure of composite resin treatments (k. collires, et al. journal of dentristy, 2018,68, 79-84.). Therefore, the mechanical properties of the dental composite resin still need to be further improved.
From the composition of the composite resin, the type, particle size, content, and the like of the inorganic filler determine the mechanical properties of the resin. However, in a complex Oral environment, silanol and ester bonds on the surface of the silanized filler are hydrolyzed (T. Nihei. journal of Oral Science,2016,58,151-155.), and the expression of the mechanical properties of the material is weakened. Compared with the mesoporous filler, the mesoporous filler can enable the organic monomer to permeate into the filler pores through the micro-mechanical interlocking effect, so that the filler surface modification process is avoided. Therefore, the application of the mesoporous filler in the dental composite resin is concerned by researchers. For example, patent CN 106038322A designs a mesoporous SiO2Coated antimicrobial fillers by silanization of SiO2The combination effectively improves the filler content and the resin mechanical property, but the maximum content of the mesoporous filler is only 10 wt%. In addition, Samuel et al use mesoporous SiO2Composite resins were prepared with a maximum loading of filler of only 40% by weight due to their high specific surface area, corresponding to a resin with a flexural strength of only 72. + -. 16MPa (S.P. Samuel, et al. Dental Materials,2009,25, 296-. Although non-porous SiO is selected2With the mesoporous SiO2The composition of the co-filler is optimized by trial and error to increase the filler amount to 70 wt%, but the minimum requirement (80MPa) of ISO 4049-2009 on the bending strength of the composite resin is not met. The above studies show that: (1) the content of the mesoporous filler in the co-filler is low, so that the advantages of the mesoporous filler are not shown to the maximum extent; (2) co-filler medium-grade spherical SiO2The particle size and the content of the compound are determined by adopting a trial-and-error method for many times, are time-consuming and labor-consuming, and are not beneficial toAnd (4) industrial production.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-strength dental composite resin and a preparation method thereof.
The invention provides a high-strength dental composite resin, which comprises raw materials of inorganic filler, organic monomer and photoinitiator, wherein the inorganic filler is a co-filler consisting of spherical mesoporous filler and spherical filler; wherein, the mass of the spherical mesoporous filler accounts for 40-55% of the total mass of the dental composite resin (the composite resin is filled with the highest content), and the mass of the spherical filler accounts for 10-25% of the total mass of the dental composite resin (the spherical mesoporous filler-based dental composite resin is filled as secondary particles with the highest addition amount).
Preferably, the spherical mesoporous filler is at least one of spherical mesoporous silica, spherical mesoporous hydroxyapatite, spherical mesoporous zinc oxide and spherical mesoporous titanium dioxide, and the particle size is 0.3-2 μm.
Preferably, the spherical filler is at least one of spherical silica, spherical hydroxyapatite, spherical zinc oxide and spherical titanium dioxide; the particle size is the maximum diameter of secondary particles obtained by using spherical mesoporous fillers as primary particles and filling the tetrahedron gaps and octahedron gaps of the spherical mesoporous fillers through an equispherical compact packing model.
Preferably, the organic monomer consists of a main monomer and a diluent monomer, and the mass of the organic monomer accounts for 20-50% of the total mass of the dental composite resin.
Preferably, the main monomer is at least one of bisphenol A-glycidyl methacrylate Bis-GMA and urethane dimethacrylate UDMA; the diluent monomer is at least one of bisethoxybisphenol-A dimethacrylate EBPADMA, triethylene glycol dimethacrylate TEGDMA, 1, 6-hexanediol diacrylate, 4-hydroxybutyl acrylate and methyl methacrylate MMA.
Preferably, the mass ratio of the main monomer to the diluent monomer is 1-4: 1.
Preferably, the photoinitiator consists of a main initiator and a co-initiator, and the mass of the photoinitiator is 1-3% of the mass of the organic monomer.
Preferably, the main initiator is at least one of camphorquinone CQ, benzophenone and diphenylethanone; the auxiliary initiator is at least one of ethyl p-dimethylaminobenzoate 4-EDMAB, trimethyl benzoyl phenyl ethyl phosphonate and methyl benzoylformate.
Preferably, the mass ratio of the main initiator to the auxiliary initiator is 1: 1-5.
The invention also provides a preparation method of the high-strength dental composite resin, which comprises the following steps:
premixing spherical mesoporous filler, organic monomer and photoinitiator, putting the mixture into a three-roll grinder for further mixing, adding spherical filler, and performing vacuum negative pressure treatment to obtain uncured composite resin paste; finally, the dental composite resin is obtained through visible light curing.
According to the invention, the spherical mesoporous filler is taken as primary particles, when the spherical mesoporous filler reaches the highest content in the composite resin, the maximum diameter of the secondary spherical particles in the internal gaps of the primary particles can be filled through theoretical calculation by using an equispherical compact packing model, and finally the particle size of the secondary spherical filler is guided in an experiment, the composition of the inorganic co-filler is optimized, and the mechanical property of the composite resin is improved.
Advantageous effects
The inorganic filler selected by the dental composite resin is a co-filler consisting of a spherical mesoporous filler and a spherical filler. The particle size of the spherical filler serving as the secondary particles is not determined by the traditional trial and error method, but is calculated by an equi-large sphere close packing model theory; the content of the mesoporous filler is the highest addition amount which can be added into the composite resin under the condition that the dental composite resin is filled with the spherical mesoporous filler to the highest degree.
The invention not only realizes the high-content filling of the spherical mesoporous filler in the composite resin, but also screens the smooth spherical filler with proper grain diameter as the secondary particle through an equispheroid close packing model to fill the gap between the spherical mesoporous fillers, thereby improving the total content of the inorganic filler and the mechanical property of the composite resin.
Drawings
FIG. 1 is a diagram of spherical mesoporous SiO in example 12TEM pictures of the particles;
FIG. 2 is a graph showing the flexural strength of the composite resin obtained in examples 1 to 3;
FIG. 3 shows the flexural moduli of the composite resins obtained in examples 1 to 3.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
(1) Composition of inorganic filler
According to the model of the close packing of the equispherical bodies, the calculation formulas of the maximum diameters of the spherical particles in the octahedral gaps and the tetrahedral gaps which can be filled with the equispherical bodies (primary particles) are respectively d80.828R and d40.45R (R is the radius of the equi-large sphere). Spherical mesoporous silica with the particle size of 550nm is selected as primary particles, and spherical silica with the particle sizes of 227nm and 123nm is selected as secondary particles according to calculation results.
(2) Preparation of composite resin
According to the formula shown in table 1, firstly, spherical mesoporous silica with the particle size of 550nm, an organic monomer and a photoinitiator are mixed by a manual premixing mode, and when the filler is fully wetted by a resin matrix, the filler is placed into a three-roll grinding machine (EXAKT 80E, Germany) for secondary mixing. Secondly, adding spherical silicon dioxide with the particle size of 227nm to the highest addition amount, and then adding spherical silicon dioxide with the particle size of 123nm to the highest addition amount. And carrying out vacuum negative pressure treatment to obtain the uncured composite resin paste. Curing for 60s by visible light (460-.
TABLE 1 Components of composite resin and contents of the components
(3) Characterization of the composite resin
The flexural strength and flexural modulus of the dental composite resin were measured by a universal tester (Instron 5900, USA) according to International Standard ISO 4049-2009, and were 122.7. + -. 6.2MPa and 9.8. + -. 1.3GPa, respectively.
Example 2
(1) Composition of inorganic filler
Spherical mesoporous zinc oxide with the particle size of 900nm is selected as the primary particle, and spherical titanium dioxide with the particle sizes of 372nm and 202nm is selected as the secondary particle according to the formula shown in the embodiment 1.
(2) Preparation of composite resin
According to the formula shown in table 2, firstly, spherical mesoporous zinc oxide with the particle size of 900nm, organic monomer and photoinitiator are mixed by adopting a manual premixing mode, and when the filler is fully wetted by the resin matrix, the filler is placed into a three-roll grinder (EXAKT 80E, Germany) for secondary mixing. Secondly, adding the spherical titanium dioxide with the particle size of 372nm to the highest addition amount, and then adding the spherical titanium dioxide with the particle size of 202nm to the highest addition amount. And carrying out vacuum negative pressure treatment to obtain the uncured composite resin paste. Curing for 60s by visible light (460-.
TABLE 2 Components of composite resin and contents of the components
(3) Characterization of the composite resin
The composite resin obtained in example 2 was characterized in the same manner as in example 1, and the flexural strength and flexural modulus of the composite resin were measured to be 131.8. + -. 5.9MPa and 10.6. + -. 1.4GPa, respectively.
Example 3
(1) Composition of inorganic filler
Spherical mesoporous silica having a particle diameter of 1.2 μm was selected as the primary particles, and spherical hydroxyapatite having a particle diameter of 496nm and 270nm, respectively, was selected as the secondary particles according to the formula shown in example 1.
(2) Preparation of composite resin
According to the formulation shown in Table 3, firstly, spherical mesoporous silica with a particle size of 1.2 μm, an organic monomer and a photoinitiator were mixed by a manual premixing method, and when the filler was sufficiently wetted by the resin matrix, the mixture was put into a three-roll mill (EXAKT 80E, Germany) for secondary mixing. And secondly, adding spherical hydroxyapatite with the particle size of 496nm to the highest addition amount, and then adding spherical hydroxyapatite with the particle size of 270nm to the highest addition amount. And carrying out vacuum negative pressure treatment to obtain the uncured composite resin paste. Then curing the mixture by visible light (460-.
TABLE 3 Components of composite resin and contents of the components
(3) Characterization of the composite resin
The composite resin obtained in example 3 was characterized in the same manner as in example 1, and the flexural strength and flexural modulus of the composite resin were measured to be 138.3. + -. 5.1MPa and 11.5. + -. 1.5GPa, respectively.
As can be seen from fig. 2 and 3, the spherical mesoporous filler and the spherical filler are selected as co-fillers to prepare the high-strength dental composite resin, wherein the particle size and the content of the mesoporous filler and the secondary spherical filler affect the mechanical properties of the composite resin. The mechanical property of the composite resin prepared in the embodiment 3 reaches the optimal value, and the bending strength of the composite resin is far more than the requirement of ISO 4049 (more than or equal to 80 MPa). The invention abandons the traditional trial-and-error method, optimizes the composition of the inorganic filler by a theoretical model calculation method, and realizes the construction of high inorganic filler content and the preparation of high-strength composite resin.
Claims (1)
1. A high-strength dental composite resin is characterized in that: the composition consists of the following components:
inorganic filler: spherical mesoporous silica 1.2 μm 52 wt%;
496nm 13 wt% of spherical hydroxyapatite;
270nm and 8 wt% of spherical hydroxyapatite;
15 wt% of organic monomer urethane dimethacrylate UDMA;
methyl methacrylate MMA 12 wt%;
the photoinitiator diphenylethanone accounts for 0.27 wt% of the mass of the organic monomer;
methyl benzoylformate 0.27 wt% with respect to the mass of the organic monomer;
the preparation method comprises the following steps:
firstly, mixing spherical mesoporous silica with the particle size of 1.2 mu m, an organic monomer and a photoinitiator in a manual premixing mode, and putting the mixture into a three-roll grinder for secondary mixing when the filler is fully wetted by a resin matrix; secondly, adding spherical hydroxyapatite with the particle size of 496nm to the highest addition amount, and then adding spherical hydroxyapatite with the particle size of 270nm to the highest addition amount; obtaining uncured composite resin paste after vacuum negative pressure treatment; and then curing the mixture by visible light to obtain the dental composite resin.
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| CN110606913B (en) * | 2019-09-11 | 2021-06-04 | 国网吉林省电力有限公司电力科学研究院 | Acrylate material capable of being rapidly cured by visible light and preparation method thereof |
| WO2021210472A1 (en) * | 2020-04-15 | 2021-10-21 | Ａｇｃエスアイテック株式会社 | Hydroxyapatite-supporting porous silica particles, method for producing hydroxyapatite-supporting porous silica particles, and composition comprising hydroxyapatite-supporting porous silica particles |
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| CN101569593B (en) * | 2009-06-02 | 2011-09-07 | 李榕卿 | Preparation method of multicomponent composite materials used for single paste type cavity filling |
| WO2012161363A1 (en) * | 2011-05-26 | 2012-11-29 | (주) 베리콤 | Dental complex composition containing crystallized glass-ceramic |
| DE112013002309B4 (en) * | 2012-08-31 | 2024-05-08 | Kettenbach Gmbh & Co. Kg | Radically polymerizable dental material, cured product and use |
| CN102895126B (en) * | 2012-11-02 | 2014-07-02 | 东华大学 | Method for preparing organic/inorganic hybrid filler for dental repair resin |
| CN108652984B (en) * | 2018-06-08 | 2019-12-31 | 东华大学 | Hydroxyapatite nanofiber reinforced silicon-based dental repair composite resin and preparation method thereof |
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| Synthesis of wrinkled mesoporous silica and its reinforcing effect for dental resin composites;Ruili Wang等;《dental materials》;20171231;第30卷;第2.2.1节，第2.2.4节，图1，表2，第3.3-3.4节 * |
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