CN108014021B - Tooth filling and repairing material and preparation method thereof - Google Patents
Tooth filling and repairing material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a tooth filling and repairing material and a preparation method thereof, belonging to the technical field of tooth materials. The tooth filling and repairing material comprises a resin matrix, an auxiliary agent, a filler and pre-polymerized resin powder; wherein the pre-polymerized resin powder is polymerized by Bis-GMA (bisphenol A Bis glycidyl methacrylate). The preparation method of the tooth filling and restoring material comprises the following steps: preparing pre-polymerized resin powder, mixing a resin matrix and an auxiliary agent, mixing the mixture A with a filler, and mixing the mixture B with the pre-polymerized resin powder. The tooth filling restoration material prepared by the invention has the bending strength of 80-120MPa after curing, the compression strength of 200-300MPa and the shrinkage rate of 1.3-2%, and compared with the prior art, the tooth filling restoration material has the advantages of excellent mechanical comprehensive performance and low shrinkage rate, and is suitable for industrial mass production.
Description
Technical Field
The invention belongs to the technical field of tooth materials, and particularly relates to a tooth filling and repairing material and a preparation method thereof.
Background
1. About dental conditions
1.1 dental diseases
With the change of the life style of the human society and the aging of the social population, the incidence rate of the dental erosion of teenagers and the dental caries of the heels and the surfaces of the teeth of the old people is increased year by year. At present, the incidence rate of the tooth erosion disease in adolescents is up to 60 percent, and epidemiological investigation research shows that the incidence rate of the people of Beijing university is 45.8 percent. According to the third national epidemiological survey report of oral health, the caries rate of the aged 65-74 years old in China is 98.4%, wherein the root-surface caries rate is as high as 63.6%. Further development of these two types of dental hard tissue diseases can lead to pulpal inflammation and local inflammation in jaw bone, even to tooth loss and extraction, and loss of masticatory function. With the development of diseases, patients not only suffer more physiological pains, but also the treatment cost is increased due to the increased difficulty of treatment in the middle and late stages of diseases, the medical burden of patients and countries is increased, and the treatment effect is rather reduced compared with the early stage of diseases.
At present, filling repair products aiming at the acid etching are almost monopolized by foreign products, the price of the products is high, and the medical burden of patients is greatly increased. The limiting factors of the material in the aspect of material science are mainly the problems of refractive index matching of the substrate and the filler, refractive index matching of the enamel and mechanical strength as close to that of the human enamel as possible; aiming at preventing root-surface caries, the filling repair material of the acid etching affected tooth and the preventing and protecting material of the root-surface caries affected tooth with independent intellectual property rights are rarely developed at home, so that the filling repair material has great social and economic benefits for improving the life quality of patients and reducing the economic counseling of the patients and the country.
Dental erosion is caused by the action of acidic substances on the tooth surface. Although dental erosion is a multifactorial disease, studies have shown that juvenile dental erosion is indistinguishable from the large number of frequently-cited carbonated beverages. The prevalence rate of the dental erosion in Europe and America is different from 20% to 71%, and the prevalence rate of the dental erosion in Qingxiao can reach 60%. For dental erosion, no mature early diagnosis technology applied to clinic exists at present. Most patients with dental erosion have come to hospital visits only if the enamel has been shown to be demineralized and defective. Current early treatments for dental erosion are dominated by demineralized enamel remineralization/enhancement and enamel defect repair techniques.
Enamel is the hardest tissue in the human body, and the main component is hydroxyapatite, which has larger resistance to chewing abrasion. Meanwhile, the enamel has unique optical properties (transparency, translucency and opalescence) so that the teeth have certain gloss and texture. Hydroxyapatite crystals in enamel affect the scattering of light, and glaze columns with different directions reflect and scatter light at different angles, so that the enamel and teeth have different color expressions. At present, the materials for repairing the enamel defects mainly comprise resin-based repairing materials and ceramic repairing materials, wherein the resin-based repairing materials and the repairing technology are widely applied to the clinical repair of the enamel defects due to the characteristics of convenient operation, excellent physical and chemical properties, flexible color selection and the like.
2. With respect to the resin matrix
2.1 resin brief introduction
Since the resin-based restorative material entered the dental restoration field in the last 60 th century, the performance of the composite resin material has been rapidly developed. The composite resin is a high molecular composite material formed by mixing inorganic filler with special treatment and bifunctional acrylate resin (such as Bis-GMA), is cured at normal temperature by means of a chemical initiation system or a light initiation system, and is usually matched with a resin-based bonding system for use. The main components of the composite resin are polymeric monomer, inorganic filler, activated diluent, polymerization initiator, accelerator, some auxiliary agents and the like. The polymerized monomer is bifunctional acrylate compound, which constitutes the main component of resin matrix, and bisphenol A-Bis (3-methacryloxy-2-hydroxypropyl) ether, namely Bis-GMA, is commonly used. Common inorganic fillers include a-quartz, silica, glass powder, porcelain powder, glass beads and the like. The inorganic filler is used for improving the mechanical strength of the composite resin material and reducing the thermal expansion coefficient, and the dosage of the inorganic filler is about 50-85% of the total weight of the composite resin. The cured composite resin material has better biological safety performance and physical and mechanical performance. The composite resin material can be blended into various colors similar to the colors of teeth according to clinical requirements, and can simulate the colors of natural teeth to a certain extent.
The existing composite resin product still has certain defects: 1) the composite resin monomer shrinks in volume during curing and may not be tightly fit with the hole wall, so that micro leakage or secondary caries is caused; 2) loss of anatomical morphology due to material wear remains a common problem with composite resin prostheses; 3) the optical refractive index of the composite resin is still different from that of a human tooth, so that a macroscopic boundary line exists between the restoration material and the tooth interface, and the attractiveness is affected. For the composite resin, how to further improve the mechanical property, reduce the condensation shrinkage and enhance the aesthetic property is a key problem concerned by scholars and materialists at home and abroad.
2.2 research progress of mouth repair Material-Photocurable composite resin
Since the 20 th 60 th generation of light-cured composite resins for oral cavity, through the development of nearly 40 years, there are many commercial products, but the properties of such resins have some defects, such as low abrasion resistance and elastic modulus, poor fitting degree, no X-ray radiation resistance, and tooth irritation after filling treatment, so that further improvement and modification are required, and the research work is mainly focused on both the resin monomer and the filler.
(1) Study of novel Main monomers
The light-cured composite resin for the oral cavity is a novel composite material proposed by Bowen at first, Bis-GMA is used as a resin matrix material, and the performance of the prepared composite resin is greatly improved compared with PMMA, so that the light-cured composite resin is widely applied to the field of oral cavity restoration. However, Bis-GMA has a large viscosity, a high water absorption value, and a large curing shrinkage, and therefore, it has been studied to synthesize a new main monomer and a resin matrix material having more excellent properties has been desired.
The viscosity of Bis-GMA reaches 1200Pa · s due to intermolecular hydrogen bonding, which is detrimental to the mixing of the matrix with the inorganic filler. The matrix viscosity is generally reduced by the addition of diluents, which tend to increase the water absorption value and cure shrinkage of the resin.
(2) Modification study of conventional fillers
The type, granularity distribution, refractive index, hardness, X-ray resistance and the volume mass percentage of the filler in the composite resin all influence the performance and clinical performance of the composite resin. In addition, in order to improve the binding force between the filler and the polymer matrix, the filler is generally subjected to silanization treatment or other surface treatment in advance to improve the interfacial binding between the filler and the matrix and improve the abrasion performance.
(3) Investigation of novel diluent monomers
For the research on novel diluent monomers, it is mainly desired to prepare monomers with small curing shrinkage, high curing degree (as judged by double bond conversion rate) and no reduction of the mechanical properties of the composite resin.
(4) Development of novel nano functional filler
In the filling material used in dentistry, since the X-ray opacity of the resin material is weak and there is no clear contrast with the tooth body of the dental caries, when the secondary caries occurs, it is difficult to distinguish the backing material, the cavity lining material or the filling material from the secondary caries on the X-ray sheet.
(5) Problems of the light-cured composite resin for oral cavity in application
At present, the use of composite resin is relatively wide in clinic, but the commonly used resin still has some problems and defects, which are mainly expressed as follows: the elastic modulus and the wear resistance are poor (compared with silver-mercury alloy), and the property can be improved by adopting the binding force of a filler or a reinforcing material with higher hardness and a resin matrix; dental pulp stimulation symptoms are caused after filling treatment, because solidification is incomplete, and residual monomers are polymerized to release heat; the secondary caries is easily caused because the resin shrinks in volume when being polymerized, and the thermal expansion coefficient is not matched with the tooth; has no X-ray resistance.
2.3Bis-GMA/(SiO2-ZrO2) Nanometer compositePreparation and performance study of synthetic resin
In modern society, the use of new materials plays an immeasurable role in the process of promoting the development of society, and the development of oral medicine is the same, so that the progress of oral cavity materials science every time can promote the oral cavity science to move forward a great step, and the development of oral cavity materials science is not provided, so that the development of modern oral cavity science is not provided. Currently, the common dental composite resin matrix monomers are: one is matrix methyl methacrylate resin (MMA) which is first applied to denture manufacture by Walter Bauer of Germany in 1937; the other two were Epoxy Resin (Epoxy Resin) as a dental Resin matrix and bisphenol a diglycidyl dimethacrylate (Bis-GMA) synthesized in 1962 as invented by the american dentist Bowen RL in 1956.
With the clinical use of methyl methacrylate, the exposed defects of large polymerization shrinkage rate, high thermal expansion coefficient, easy color change, damage to dental pulp, easy formation of secondary caries and the like are gradually discovered. MMA has been gradually replaced with bisphenol A diglycidyl methacrylate (Bis-GMA) resin due to its excellent properties since the invention. At present, the most used is that the diluent monomer is triethylene glycol dimethacrylate (TEGDMA) which is used as the diluent monomer and is added into Bis-GMA to be used as matrix resin together. In the matrix resin, the TEGDMA has the functions of dissolving and diluting, and simultaneously has the function of cross-linking polymerization, thereby improving the performance of the composite resin.
The main components of the composite resin are a resin matrix and an inorganic filler, wherein the type, the quantity, the particle size distribution and the like of the inorganic filler have important influences on various properties of the material, and the density, the tensile strength, the hardness, the toughness, the mechanism and the like of the composite material are mainly influenced. The method of surface treatment is a feasible way to improve the interface performance of the composite material. The exploration of the nano filler reinforced composite material is always the research focus of the composite material academic community in the last two decades.
2.4 high-strength resin dental material and preparation method thereof
The prior commonly used resin material for teeth is mainly polymerized by methyl methacrylate monomer and methyl methacrylate, and is used as resin teeth and resin denture powder base material and the like in stomatology; when in use, the material is not wear-resistant, has poor strength and color, is easy to yellow and break; the combination of the acrylic resin tooth and the acrylic resin base is poor, and the phenomenon of falling is easy to occur; similar problems also exist in the "dental resin composition" disclosed in chinese patent publication No. CN1196923A and the "metal reinforced composite resin" disclosed in publication No. CN1210713A, in the case where a trace amount of rare earth element is not added.
2.5 nanometer fluorine-containing resin dental material and preparation method thereof
Modern dental materials generally use polymerizable monomers, mostly methacrylates, in combination with inorganic fillers and polymerization initiators. Since the invention of BisGMA monomer by Rafael L.Bowen, the material is developed rapidly, and is widely used for dental filling materials, crowns, point bridges, admixtures, embedding materials, external embedding materials, repair of artificial teeth and porcelain teeth, and the like. However, as people become more aware of oral cavity materials, demands on dental materials are increasing. Not only is it required to have a specific strength and other functions, but also it is required to have biological activity, antibacterial and anticaries properties, so that the multifunctional resin material is a new product development direction. In the future market, only such multifunctional materials can meet the needs of people.
Many studies have demonstrated that if the material of the dental filling has the ability to release fluoride ions, secondary caries at the edges of the filling is significantly reduced. The main reasons for this are: the fluoride ions released by the material can diffuse into the hard tissues of adjacent teeth and combine with hydroxyapatite in the tooth body, thereby improving the anti-caries capability of the hard tissues of the teeth. In the long-term clinical research practice, it is found that in the fifth type of dental caries repair, if there are micro-cracks in dentin, secondary caries occurs much less than when a fluorine-free composite resin is used alone using a glass plasma cement. The reason for this is that the former can release fluoride ions, which improves the anticaries ability of teeth. The introduction of fluorine-containing inorganic salts into composite resins can lead to deterioration of the mechanical properties of the materials due to their poor compatibility with the resin matrix.
The polishing performance and the wear resistance of the composite resin can be greatly improved by using the nano powder, but the self-aggregation of the nano powder can obviously influence the flowing behavior and the clinical operation hand feeling of the material, so that the material rheology is unstable, namely the viscosity of the material can change along with the operation time. More importantly, this self-aggregation behavior can lead to uneven distribution of the powder in the resin matrix, and the resulting aggregated domains of the nanopowder can act as the origin or region of stress cracking. Therefore, it is very important to disperse the nano powder well. The existing dispersing technology comprises three-axis roller milling, ultrasonic oscillation, pneumatic high-speed dispersion and the like, but the existing dispersing technology is not economical and efficient.
2.6 preparation method and application of dental composite resin containing functional monomer PMDM and modified hydroxyapatite
In the late 20 th century, 80 s, authoritative journals had optimistically predicted that caries could be controlled and could become another, obliterative, disease. The world health organization's survey of epidemics does not support this conclusion, however, and statistical results show that the prevalence of caries is high in some underdeveloped countries. At present, the per-capita caries rate of China is 40%, wherein the per-capita caries rate of children is 80%, the per-capita caries rate is 60-70%, the old caries rate is 52%, each patient relates to 2-3 teeth on average, and the prevalence rate of the periodontitis and the periodontitis is 70%. The large demand for dental filling materials indicates that dental filling materials have a great market prospect. The traditional composite resin is a tooth repair material formed by combining an organic resin matrix, an inorganic filler and an initiating system, is an essential important material for replacing silver amalgam for tooth defect repair treatment, and is widely used for direct and indirect repair treatment of various tooth defects.
The ideal composite resin for oral cavity restoration has the advantages of higher mechanical strength, thermal expansion coefficient similar to that of teeth, smaller polymerization shrinkage, certain cohesiveness, good polishing performance, insolubility in saliva, color similar to that of teeth and the like. However, the composite resin produced at home and abroad, especially at home, still has major problems in some aspects, such as lower strength of the composite resin compared with silver-mercury alloy, large polymerization shrinkage and the like. In recent years, as doctors and patients have increasingly demanded to simplify the procedure of clinical operation in the oral cavity, the demand for the properties of the oral cavity repair resin itself has been increasing. Conventional restorative resins are not adhesive and when they are filled into teeth for restorative action, if not assisted by an adhesive, will easily cause marginal microleakage. Therefore, research and development of cheap and efficient dental composite resin have important clinical significance, but at present, domestic dental composite resin with independent intellectual property rights and low price is relatively few, most of the clinical use is imported dental composite resin, domestic brands have few products, but all the products have advantages and disadvantages, and a product with excellent comprehensive performance is not available.
2.7 dental Material, dental Material composition, dental restorative Material, and cured product
Conventionally, radical polymerizable monomers represented by (meth) acrylates have been widely used in various fields such as paints, printing plates, optical materials, and dental materials, taking advantage of their excellent properties such as curability and transparency.
In the field of dental materials, the present invention is widely applied to dental restorative materials such as dental composite resins used for restorations of dental caries, fracture and the like of natural teeth, various dental adhesives used for bonding dental composite resins to teeth, artificial gum materials and the like.
The dental composite resin is generally composed of a polymerizable monomer, a polymerization initiator, and a filler, and as the polymerizable monomer, a radical polymerizable polyfunctional (meth) acrylate is used from the viewpoints of safety in vivo, mechanical strength of a cured product, abrasion resistance, and aesthetic appearance. 2, 2-Bis [ 4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl ] propane (commonly known as Bis-GMA), 2, 4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate (commonly known as UDMA) were used as the polyfunctional (meth) acrylate, and Bis-GMA in particular has been used as a polymerizable monomer for almost all dental composite resins since its application to dental materials was first proposed by Bowen in 1962.
However, in the dental composite resin, it has been clinically pointed out that there is a large room for improvement in the flexural strength, elastic modulus and abrasion resistance of a cured product, reduction in water absorption and discoloration, reduction in polymerization shrinkage during curing, transparency and aesthetic properties similar to those of natural teeth, and the like. In particular, shrinkage due to polymerization shrinkage causes shrinkage joints generated by peeling of the dental composite resin from the adhesive surface, and causes secondary caries, pulp irritation, coloring, removal of restorations, and the like, and therefore, it is strongly desired to reduce the shrinkage joints as much as possible. In addition, in order to satisfy high requirements for aesthetic properties and impart X-ray contrast properties, fillers having a high refractive index are often used in dental composite resins, and therefore, it is necessary to impart transparency close to that of natural teeth, and it is desirable that the refractive index of the polymerizable monomer used is high. Further, from the viewpoint of durability (impact resistance and fracture resistance) in the oral cavity, it is desired to have high flexural strength.
For the reduction of polymerization shrinkage, it has been proposed to use a ring-opening polymerizable epoxy compound or oxetane compound having polymerization shrinkage generally smaller than that of an acrylic compound (dawn et al, research progress on an oral cavity repair material-photocurable composite resin, material report 2006, 20(5), 44). Although the use of these compounds tends to reduce the polymerization shrinkage, there are many problems such as the need for a special primer (primer) because of the difference in curing system. Further, there is a problem from the viewpoint of appearance and workability.
In addition, it has been proposed to reduce polymerization shrinkage by increasing the filler loading (Zutongqing et al, preparation and performance studies of Bis-GMA/(SiO2-ZrO2) nanocomposite resin, J.Med.Physics, China, 2014,31(3), 4957; Lixiao-shaped, high strength resin dental material and its preparation method, publication No. CN 1456142A). However, since the shrinkage of the monomer used is large, the effect thereof is limited.
Also proposed is the use of a silicon-containing (meth) acrylate low shrinkage material (Malrongtang, Yan Steel, Yan Peng, Sche, Nano fluorine-containing resin dental material and its preparation method, publication No. CN 101721316A). However, the synthesis of this material is cumbersome, leaving problems in terms of industrial production. Further, there is a problem also from the viewpoint of the mechanical strength of the cured product.
Therefore, there is a demand for a polymerizable monomer which can be used for a dental restorative material, has a small polymerization shrinkage during curing, and can be industrially produced at a low cost.
2.8 preparation method of novel light-cured composite resin material for oral cavity
Oral cavity complex resins were developed as restorative materials for posterior teeth in the mid-sixties of the last century. In recent years, composite resins have been developed rapidly and their applications have become more and more widespread.
The composite resin is mainly formed by combining an organic resin matrix and an inorganic filler, and generally mainly comprises four parts: (1) the organic matrix phase consists of a polymerizable monomer system, a photoinitiation system capable of initiating free radical polymerization reaction, a stabilizer for prolonging the shelf life of the composite resin and the like; (2) inorganic fillers, generally glass powder, quartz powder or fumed silica and the like; (3) coupling agents, generally organosilicon compounds, capable of linking the organic matrix and the inorganic filler together by chemical bonds; (4) and a photoinitiation system for initiating the free radical polymerization reaction.
Although each of the above components has an effect on the final properties of the composite resin, the main effect on the mechanical properties and the shrinkage of the composite resin is the organic matrix. Scientists have therefore conducted a great deal of research in recent years on the monomers and oligomers of the organic matrix of composite resins.
Bisphenol A Bis glycidyl methacrylate (Bis-GMA) was the earliest monomer of the composite resin and was the most widely used monomer. Many of the composite resins appearing in the market are based on Bis-GMA and show excellent clinical performance. Bis-GMA also has a plurality of defects, which are mainly shown in the following points: (1) the composite resin is easy to absorb water, the mechanical property of the composite resin is reduced due to the water absorption, and the service life of the composite resin is shortened; (2) the conversion rate of double bonds is not high, the mechanical strength is in a certain relation with the conversion rate, generally, the higher the conversion rate is, the larger the mechanical strength is, and the improvement of the conversion rate can reduce the leakage of unpolymerized monomers; (3) polymerization shrinkage is high, which can lead to the formation of edge cracks between the composite resin and the tooth body and finally to the formation of edge microleaks; (4) too high a viscosity results in an influence on the amount of filler added, and accordingly on the mechanical properties of the composite resin.
The commonly used tooth filling material is silver-mercury alloy, and has the characteristics of strong operability, excellent mechanical property and wear resistance. However, the color and luster of the silver-mercury alloy are not consistent with the tooth structure, and the potential mercury toxicity problem is gradually attracting attention. The composite resin as a novel oral cavity repairing material is a tooth repairing material which is formed by combining an organic resin matrix, an inorganic filler and an initiating system, has the advantages of higher mechanical strength, similar thermal expansion coefficient with teeth, no dissolution in saliva, similar color and luster with teeth and the like, and is widely applied to the repairing and filling of caries. The inorganic filler used in the composite resin is selected from materials such as crystal quartz, fumed silica, barium aluminum borate silicate glass and the like. However, the existing composite resin still has the defects of insufficient mechanical strength, poor wear resistance, large polymerization volume shrinkage and the like in actual use.
The hydroxyapatite is a main inorganic substance forming the hard tissue of the human body, has no toxicity, no stimulation, no adverse reaction, good biocompatibility and bioactivity, has polarity on the surface, can be combined with human body cells, polysaccharide and protein by hydrogen bonds, and has strong affinity with the body tissue. The hydroxyapatite not only can play a role of a bracket for calcium salt deposition, but also can induce the formation of new bones, can directly form bonding with soft and hard tissues of a human body, and plays an increasingly important role in repairing and replacing materials. The nano hydroxyapatite can directly seal the glaze surface gap formed by demineralization, and has good remineralization effect. Meanwhile, the hydroxyapatite crystal also has the function of adsorbing and removing components such as protein, amino acid, lipid, glucan and the like which form dental plaque on the surface of teeth.
The performance of the composite resin is greatly influenced by factors such as the type, performance, particle size distribution, content in the resin, combination with a resin matrix and the like of the inorganic filler, and is mainly reflected in two aspects of physical performance and mechanical performance. The inorganic filler in the existing composite resin is generally quartz filler, has a larger contact angle with water, low water absorption, reduced micro-leakage, stronger surface contamination resistance and relatively poorer physical and mechanical properties. Meanwhile, the composite resin has certain polymerization shrinkage, and the polymerization shrinkage of the composite resin seriously damages the edge sealing of the restoration, so that the bonding of the interface of the tooth restoration is damaged. The existing preparation method has a plurality of limitations, such as: the process is too complex, the period is long, and the operability is poor.
Based on the above background, the shrinkage index has a significant effect on the use of the dental restorative material in actual dentistry: the excessive shrinkage of the resin can directly affect the mechanical property, the prevention of decayed teeth and the beauty of the material, and under the condition of not affecting other mechanical strength indexes of a resin matrix, the invention of the resin capable of ensuring the low shrinkage rate is necessary.
Disclosure of Invention
The invention aims to provide a tooth filling and repairing material and a preparation method thereof. The product adopts the light-cured resin, is assisted by the pre-polymerized resin powder, and adopts the structure-reinforced particle technology (such as nano silicon dioxide or zirconium oxide), the reinforcing technology of the existing product adopts the addition of nano silicon dioxide or zirconium oxide, and the product has the characteristics of quick curing, good polishing performance, low shrinkage, good mechanical strength, wear resistance and excellent biocompatibility, and is suitable for the tooth filling and repairing material with I and II defects of human teeth.
In order to achieve the purpose, the invention adopts the following technical scheme:
a tooth filling and repairing material comprises a resin matrix, an auxiliary agent, a filler and pre-polymerized resin powder; the pre-polymerized resin powder is polymerized by Bis-GMA (bisphenol A Bis glycidyl methacrylate).
In the above dental filling and restoration material, as a preferred embodiment, the pre-polymerized resin powder comprises Bis-GMA and a first initiator as main components; the reason for adding the pre-polymerized resin powder to the dental filling restoration material is as follows: firstly, a part of Bis-GMA can be replaced, and the addition amount of the Bis-GMA is relatively reduced; the Bis-GMA in the pre-polymerized resin powder and the Bis-GMA added in the resin matrix are resins, and the mechanical property of the tooth filling restoration material obtained by the method cannot be influenced; secondly, the shrinkage rate of the tooth filling and repairing material can be ensured, the shrinkage rate is reduced, and the part of Bis-GMA of the pre-polymerized resin powder is polymerized before the resin is used for light curing so as to ensure that the shrinkage can not occur again in the resin light curing process; moreover, the polymerization conditions of the Bis-GMA resin in the pre-polymerized resin powder are controllable, and the mechanical properties of the polymerized Bis-GMA monomer can reach the best. The tooth filling and repairing material prepared by the material preparation method not only increases the mechanical property, but also reduces the influence of shrinkage stress on resin.
At present, most of resin repair materials used in the market adopt acrylic acid modified resin, Bis-GMA is the most main component in a resin formula, and the mechanical strength of the monomer after synthesis is higher than that of other acrylic acid modified resin, so that the Bis-GMA is adopted as a base material of pre-polymerized resin powder. The Bis-GMA is used for preparing the pre-polymerized resin powder, the polymerization shrinkage of the pre-polymerized resin powder already occurs in the pre-polymerization process, and the self shrinkage of the powder is very low. Meanwhile, the addition amount of Bis-GMA in the resin matrix part can be reduced, and the filling shrinkage rate is reduced in the using process of the product.
In the above dental filling and restoring material, as a preferred embodiment, the contents of the respective components in the dental filling and restoring material in mass fraction are as follows: 10-20% of resin matrix, 0.1-0.5% of auxiliary agent, 55-65% of filler and 20-30% of pre-polymerized resin powder; preferably, the resin matrix is 15.7 percent, the auxiliary agent is 0.3 percent, the filler is 59 percent, and the pre-polymerized resin powder is 25 percent.
In the above dental filling and restoring material, as a preferred embodiment, the dental filling and restoring material is a viscous gel.
In the above dental filling/restoration material, the particle size of the pre-polymerized resin powder is preferably 0.1 to 10 μm, and the particle size of the pre-polymerized resin powder is preferably 0.1 to 1 μm, and more preferably 0.4 μm. The pre-polymerized resin powder mainly functions to reduce the shrinkage of the dental filling restoration material.
In the above dental filling and restoration material, as a preferred embodiment, the resin matrix is an acrylic-modified bisphenol a resin and/or an acrylate resin; preferably, in the dental filling and restoration material, the content of the acrylic acid modified bisphenol A resin is 5-8% and the content of the acrylate resin is 5-12% by mass; more preferably, the content of the acrylic acid modified bisphenol A resin is 6%, and the content of the acrylate resin is 10%. The bisphenol A modified acrylic resin is the main resin for realizing the mechanical strength of the existing resin, is the main component of the existing resin matrix, and other modified acrylic resins are basically supplements for the defects of processing aspects of the bisphenol A modified acrylic resin. In order to ensure that more fillers can be added into the resin, a certain amount of matched resin with lower viscosity, good processing performance and not too poor mechanical strength after reaction needs to be added.
In the above dental filling and restoration material, as a preferred embodiment, the acrylic-modified bisphenol a resin is bisphenol a Bis glycidyl methacrylate (Bis-GMA) and/or ethoxybisphenol a Bis methacrylate (Bis-EMA); the acrylate resin is dimethacrylate (UDMA, CAS number 72869-86-4, English name urethane dimethacrylate) and/or Triethylene glycol dimethacrylate (TEG-DMA, CAS number 109-16-0, English name Triethylene glycol dimethacrylate); more preferably, in the dental filling restoration material, the content of the diisocyanate dimethacrylate is 4% and the content of the triethylene glycol dimethacrylate is 6% by mass.
In the above dental filling and restoration material, as a preferred embodiment, the mass fraction of the bisphenol a Bis glycidyl methacrylate (Bis-GMA) in the resin matrix in the dental filling and restoration material is 6%, and the refractive index of the Bis-GMA is 1.552.
In the above dental filling and restoration material, as a preferred embodiment, the auxiliary agent includes a photoinitiator, a polymerization initiator, and a polymerization inhibitor; the resin repairing agent can also comprise a chemical initiator, the mechanical property of the resin repairing agent can be better ensured by adopting photo-initiation and chemical-initiation double polymerization, and a certain amount of polymerization inhibitor is added to ensure certain operation time in the actual use process. Preferably, the mass fraction of the photoinitiator in the dental filling restoration material is 0.04%, the mass fraction of the polymerization initiator in the dental filling restoration material is 0.25%, and the mass fraction of the polymerization inhibitor in the dental filling restoration material is 0.01%.
In the above dental filling and restoring material, as a preferred embodiment, the photoinitiator is one or more of camphorquinone, a cleavage type initiator, and a cationic initiator (such as onium salt); preferably, the photoinitiator is camphorquinone; the polymerization inhibitor is preferably one or more of p-hydroxy xylene, phenols, quinones and aromatic nitro compounds; more preferably, the polymerization inhibitor is p-hydroxyxylene. The polymerization initiator is one or a mixture of ETH (isooctyl p-dimethylaminobenzoate) and phenoxy ketone; more preferably, when the polymerization initiator is a mixture of ETH and phenoxy ketone, the mass fraction of ETH in the dental filling restoration material is 0.18%, and the mass fraction of phenoxy ketone in the dental filling restoration material is 0.07%.
In the above dental filling and restoring material, as a preferred embodiment, the filler is composed of a nanoparticle filler and a glass powder; the nano particle filler is preferably nano silica particles, and the main function of the nano silica is to increase the mechanical strength of the material; the main functions of the glass powder are to increase the abrasion resistance and improve the optical effect.
More preferably, the particle size of the nano silicon dioxide particles is one or more of 10nm, 50nm and 100 nm; further, the mass fraction of the nano-silica particles with the particle size of 10nm in the tooth filling and restoring material is 3%, the mass fraction of the nano-silica particles with the particle size of 50nm in the tooth filling and restoring material is 6%, and the mass fraction of the nano-silica particles with the particle size of 100nm in the tooth filling and restoring material is 3%. The reason for the reinforcement after mixing with silica of different particle sizes is as follows: on one hand, particles with small particle size have larger comparative area, are difficult to add singly and cannot be added in large quantity, and the excessive addition amount has certain influence on the shrinkage rate of the tooth filling and repairing material; on the other hand, the particles with larger particle size can not achieve better wear resistance and mechanical property by singly using the particles; thus, a wide particle size range has certain benefits for balancing the two.
More preferably, the glass powder is one or a mixture of glass powder with a particle size of 0.4 μm and glass powder with a particle size of 2 μm; the reason for using glass powder of different particle size is the same as that for using silica of different particle size. Further, the glass powder having a particle size of 0.4 μm was present in the dental filling restoration material at a mass fraction of 40%, and the glass powder having a particle size of 2 μm was present in the dental filling restoration material at a mass fraction of 7%.
The preparation method of the tooth filling and repairing material comprises the following steps:
preparation of prepolymerized resin powder: preparing Bis-GMA resin and a first initiator by a solid method to obtain pre-polymerized resin powder;
mixing the resin matrix with the auxiliary agent: stirring and mixing the resin matrix and the auxiliary agent to obtain a mixture A;
mixing the mixture A with a filler: adding a filler into the mixture A, and stirring and mixing to obtain a mixture B;
mixture B was mixed with prepolymerized resin powder: adding pre-polymerized resin powder into the mixture B, and stirring and mixing to obtain the tooth filling and repairing material;
in the preparation method, the raw materials are weighed according to the mass fraction of each component relative to the total amount of the raw materials of the tooth filling and restoring material, wherein the weight percentages of the resin matrix, the auxiliary agent, the filler and the pre-polymerized resin powder are respectively 10-20 wt%, 0.1-0.5 wt%, 55-65 wt% and 20-30 wt%.
In the above production method, as a preferable embodiment, in the preliminary polymerized resin powder production step, the first initiator is Benzoyl Peroxide (BPO), Azobisisobutyronitrile (AIBN), or the like; preferably, the first initiator is Benzoyl Peroxide (BPO), and further, the amount of the benzoyl peroxide is 0.2% of the mass of the Bis-GMA resin.
In the above production method, as a preferred embodiment, in the preliminary polymerization resin powder production step, the solid production conditions are as follows: mixing Bis-GMA resin with a first initiator, exhausting a reaction system for 10-20 min until the vacuum degree is-0.05 to-0.1 Mpa (preferably-0.1 Mpa, namely the reading of a vacuum meter is-0.1 Mpa), stirring for 3-8 h at 25-55 ℃, then heating for polymerization, and carrying out post-treatment to obtain the pre-polymerization resin powder.
More preferably, in the preparation conditions of the solid-phase method, the polymerization initiation temperature in the temperature-rising polymerization is 60-70 ℃, and the polymerization time is 3-8 h.
More preferably, in the solid-phase preparation conditions, the post-treatment is as follows: cooling the reaction system after polymerization to room temperature, circularly crushing, ball-milling, drying and sieving, and taking undersize as pre-polymerization resin powder; further, the number of times of circulating crushing is 2-5 times; the ball milling time is 60-120min, preferably 60 min; the drying time is 2-6 h, and the drying temperature is 80-120 ℃; the mesh number of the sieved screen is 600-1500 meshes.
In the above preparation method, as a preferred embodiment, in the step of mixing the resin matrix with the auxiliary agent, the resin matrix is mixed with the photoinitiator, the polymerization initiator and the polymerization inhibitor under stirring, wherein the stirring speed is 3 to 10r/min and the stirring time is 20 to 40 min; preferably, the photoinitiator is camphorquinone, the polymerization initiator is ETH and/or phenoxy ketone, and the polymerization inhibitor is p-hydroxy xylene.
In the above preparation method, as a preferred embodiment, the step of mixing the mixture a with the filler is specifically performed as follows: adding nano silicon dioxide powder into the mixture A, and stirring and mixing at the stirring speed of 3-10 r/min for 10-20 min; then adding glass powder, stirring and mixing at the stirring speed of 3-10 r/min for 10-20 min to obtain a mixture B. The nano silicon dioxide powder has smaller granularity and is preferentially added under the condition of lower material viscosity so as to improve the dispersion degree.
In the above production method, as a preferred embodiment, the mixing step of the mixture B with the prepolymerized resin powder comprises, in order: step one, adding the pre-polymerized resin powder into the mixture B, stirring and mixing at a stirring speed of 5-20 r/min for 30-60 min; continuously stirring under the vacuum condition, wherein the stirring speed is 3-10 r/min, and the stirring time is 10-20 min; thirdly, finishing the reaction system under normal pressure, and continuing stirring at the stirring speed of 5-20 r/min for 30-60 min; fourthly, vacuumizing again and stirring continuously, wherein the stirring speed is 5r/min, and stirring is continuously carried out at the speed of 15-30 r/min within 5min until the vacuum degree is pumped to-0.05-0.1 Mpa and the stirring is continuously carried out at the vacuum degree (namely the reading of a vacuum meter) of-0.05-0.1 Mpa for 14-16 min; and fifthly, reversely stirring under a vacuum condition, wherein the stirring speed is 3-10 r/min, the stirring time is 5-10min, and obtaining the tooth filling and repairing material after stirring.
Compared with the prior art, the invention has the following technical benefits:
the invention discloses a novel tooth filling and repairing material and a preparation method thereof. The novel tooth filling and repairing material has the characteristics of rapid curing, good polishing performance, low shrinkage rate, good mechanical strength, wear resistance and excellent biocompatibility, the product is prepared by adopting a photocuring process and assisting with a pre-polymerized resin powder and structure-enhanced particle technology, the photocuring time is 3-10min, the bending strength after curing is 80-120MPa, the compression strength is 200-300MPa, and the shrinkage rate is 1.3-2%, so that the novel tooth filling and repairing material is suitable for repairing I and II type defects of teeth. Compared with the prior art, the product of the invention has excellent mechanical comprehensive performance and low shrinkage rate, and is suitable for industrial mass production.
Detailed Description
The dental filling restoration material and the preparation method thereof according to the present invention will be described with reference to examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. It should be understood that various changes and modifications can be made by those skilled in the art after reading the disclosure of the present invention, and equivalents fall within the scope of the appended claims.
Raw materials used for preparing the tooth filling restoration material such as Bis-GMA, UDMA, TEG-DMA, camphorquinone, ETH, phenoxy ketone, p-hydroxy xylene, nano silicon dioxide particles, glass powder, benzoyl peroxide, AIBN and the like belong to commercial products.
Wherein the molecular formula of Bis-GMA is shown as formula I:
the molecular weight is 512.59, CAS No. 1565-94-2.
Examples 1 to 4
The raw materials and the amounts used in examples 1 to 4 are shown in Table 1; wherein the feeding amount of each component is calculated according to the mass fraction of the component in the tooth filling and restoring material.
Examples 1-4 dental filling restorative materials were prepared in the same manner, specifically as follows:
(1) preparation of prepolymerized resin powder: mixing Bis-GMA resin monomer with initiator Benzoyl Peroxide (BPO) 0.2 wt%, stirring at 50 deg.C for 5hr, and exhausting for 15min to obtain vacuum degree of-0.1 Mpa. Pouring the mixture into a tray after stirring, wherein the thickness of the mixture is 10-20mm, and covering the tray with an aluminum foil. After pouring, the tray was put into an oven to be polymerized at a polymerization initiation temperature of 65 ℃ for 5 hr. And (3) cooling the material to room temperature after polymerization, taking out the material covered on the tray, crushing the material by using a jaw crusher, and circularly crushing for 3 times. Ball-milling and mixing the crushed materials in a ball mill for 60-120min, drying the powder after the ball milling is finished, wherein the drying time is 2hr, the drying temperature is 100 ℃, then, sieving the powder by a 1000-mesh sieve, and taking the undersize product, namely the pre-polymerized resin powder, wherein the weight average molecular weight (Wm) of the pre-polymerized resin powder is 10000-100000.
(2) Mixing the resin matrix and the auxiliary agent: and simultaneously pouring the resin matrix, the photoinitiator, the polymerization initiator and the polymerization inhibitor into a double-planet stirrer for stirring and mixing, wherein the stirring speed is 5 revolutions per minute, and the stirring time is 30min, so as to obtain a mixture A.
(3) Mixing of mixture a and filler: and adding 10nm, 50nm and 100nm nano silicon dioxide particles into the mixture A, stirring at the speed of 5r/min for 15min, and then adding 0.4 mu m and 2 mu m glass powder into the mixture A, stirring at the speed of 5r/min for 15min to obtain a mixture B.
(4) Mix B and pre-polymerized resin powder mix: and adding the pre-polymerized resin powder into the mixture B, and stirring at the speed of 10 revolutions per minute for 40 min. Vacuumizing, keeping the stirring speed at 5 revolutions per minute, finishing the resin after stirring for 15min, continuously stirring at the stirring speed of 10 revolutions per minute for 40min, vacuumizing again at the stirring speed of 5 revolutions per minute, and continuously vacuumizing until the lowest pressure (-0.1MPa) is required to be pumped within 5min, and continuously stirring at the vacuum degree at the speed of 20 revolutions per minute for 15 +/-1 min; and then, continuously stirring under the vacuum degree of 10Pa, and obtaining the tooth filling restoration material after stirring at the stirring speed of 5 revolutions per minute for 7min, wherein the stirring is required to be reversed.
The tooth restoration material was subjected to mechanical property tests, and the test results are shown in table 2.
Table 1 composition table of repair material raw materials (% by mass)
TABLE 2 Properties of the repair materials obtained in the examples
Claims (27)
1. A tooth filling and repairing material is characterized by comprising a resin matrix, an auxiliary agent, a filler and pre-polymerized resin powder; the pre-polymerized resin powder is prepared from Bis-GMA resin and a first initiator through a solid method; wherein the content of the first and second substances,
the preparation conditions of the solid method are as follows: mixing Bis-GMA resin with a first initiator, exhausting a reaction system for 10-20 min until the vacuum degree is-0.1 Mpa, stirring for 3-8 h at 25-55 ℃, then heating for polymerization, and performing post-treatment to obtain the pre-polymerization resin powder, wherein in the heating for polymerization, the polymerization initiation temperature is 60-70 ℃, and the polymerization time is 3-8 h;
the particle size of the pre-polymerized resin powder is 0.1-1 mu m;
the first initiator is benzoyl peroxide or azobisisobutyronitrile;
the dental filling and repairing material comprises the following components in percentage by mass: 10-20% of resin matrix, 0.1-0.5% of auxiliary agent, 55-65% of filler and 20-30% of pre-polymerized resin powder;
the resin matrix is acrylic acid modified bisphenol A resin and acrylate resin; the acrylic acid modified bisphenol A resin is bisphenol A bis glycidyl methacrylate and/or ethoxy bisphenol A bis methacrylate; the acrylate resin is dimethacrylate diisocyanate and/or triethylene glycol dimethacrylate; in the tooth filling and repairing material, the mass percent of the acrylic acid modified bisphenol A resin is 5-8%, and the mass percent of the acrylate resin is 5-12%;
the auxiliary agent comprises a photoinitiator.
2. The dental filling restoration material according to claim 1, wherein the dental filling restoration material comprises the following components in percentage by mass: 15.7 percent of resin matrix, 0.3 percent of auxiliary agent, 59 percent of filler and 25 percent of pre-polymerized resin powder.
3. The dental filling restoration material according to claim 1, wherein the pre-polymerized resin powder has a particle size of 0.4 μm.
4. The dental filling restoration material according to claim 1, wherein the acrylic-modified bisphenol a resin is present in an amount of 6% by mass and the acrylic ester resin is present in an amount of 10% by mass in the dental filling restoration material.
5. The dental filling restoration material according to claim 4, wherein the acrylate resin is the dimethacrylate and the triethylene glycol dimethacrylate, and wherein the mass percentage of the dimethacrylate and the mass percentage of the triethylene glycol dimethacrylate are 4% and 6%, respectively.
6. The dental filling restoration material according to claim 4, wherein the acrylic modified bisphenol A resin is the bisphenol A bis glycidyl methacrylate, and the mass percentage of the bisphenol A bis glycidyl methacrylate in the dental filling restoration material is 6%.
7. The dental filling restoration material according to claim 1, wherein the auxiliary agent further comprises a polymerization initiator and a polymerization inhibitor.
8. The dental filling restoration material according to claim 7, wherein the photoinitiator is present in the dental filling restoration material in an amount of 0.04% by mass, the polymerization initiator is present in the dental filling restoration material in an amount of 0.25% by mass, and the polymerization inhibitor is present in the dental filling restoration material in an amount of 0.01% by mass.
9. The dental filling restoration material according to claim 8, wherein the photoinitiator is one or more of camphorquinone, a cleavage type initiator, and a cationic initiator.
10. The dental filling restoration material according to claim 9, wherein the photoinitiator is camphorquinone; the polymerization inhibitor is one or more of p-hydroxy xylene, phenols, quinones and aromatic nitro compounds.
11. The dental filling restoration material according to claim 10, wherein the polymerization inhibitor is p-hydroxyxylene; the polymerization initiator is one or a mixture of ETH and phenoxy ketone.
12. The dental filling restoration material according to claim 11, wherein when the polymerization initiator is a mixture of ETH and phenoxy ketone, the ETH is 0.18% by mass and the phenoxy ketone is 0.07% by mass in the dental filling restoration material.
13. The dental filling restoration material according to claim 1, wherein the filler is composed of a nanoparticle filler and a glass powder.
14. The dental filling restoration material according to claim 13, wherein the nanoparticle filler is nanosilica particles.
15. The dental filling restoration material according to claim 14, wherein the nanosilica particles have a particle size of one or more of 10nm, 50nm and 100 nm.
16. The dental filling restoration material according to claim 15, wherein the nanosilica particles having a particle size of 10nm are present in the dental filling restoration material in a percentage by mass of 3%, the nanosilica particles having a particle size of 50nm are present in the dental filling restoration material in a percentage by mass of 6%, and the nanosilica particles having a particle size of 100nm are present in the dental filling restoration material in a percentage by mass of 3%.
17. The dental filling restoration material according to claim 13, wherein the glass powder is one or a mixture of glass powder having a particle size of 0.4 μm and glass powder having a particle size of 2 μm.
18. The dental filling restoration material according to claim 17, wherein the glass powder having a particle size of 0.4 μm is present in the dental filling restoration material at 40% by mass and the glass powder having a particle size of 2 μm is present in the dental filling restoration material at 7% by mass.
19. The dental filling restoration material according to claim 3, wherein the dental filling restoration material is a viscous gel.
20. The method for preparing a dental filling restoration material according to any of claims 1-19, comprising the steps of:
preparation of prepolymerized resin powder: preparing Bis-GMA resin and a first initiator by a solid method to obtain pre-polymerized resin powder; wherein the first initiator is benzoyl peroxide or azobisisobutyronitrile;
mixing the resin matrix with the auxiliary agent: mixing the resin matrix and the auxiliary agent according to any one of the proportions of claims 1 to 19 under stirring to obtain a mixture A;
mixing the mixture A with a filler: adding a filler into the mixture A according to the proportion of any one of claims 1 to 19, and stirring and mixing to obtain a mixture B;
mixture B was mixed with prepolymerized resin powder: adding the pre-polymerized resin powder to the mixture B according to the ratio of any one of claims 1 to 19, and stirring and mixing to obtain the dental filling and restoration material.
21. The method according to claim 20, wherein the benzoyl peroxide is 0.2% by mass of the Bis-GMA resin in the preparation of the pre-polymerized resin powder.
22. The method of claim 20, wherein the solid-phase preparation conditions are as follows: mixing Bis-GMA resin with a first initiator, exhausting a reaction system for 10-20 min until the vacuum degree is-0.1 Mpa, stirring for 3-8 h at 25-55 ℃, then heating for polymerization, and performing post-treatment to obtain the pre-polymerization resin powder, wherein in the heating for polymerization, the polymerization initiation temperature is 60-70 ℃, and the polymerization time is 3-8 h;
the post-treatment is as follows: and cooling the reaction system after polymerization to room temperature, and performing circulating crushing, ball milling, drying and sieving to obtain the pre-polymerized resin powder.
23. The production method according to claim 22, wherein the number of the cyclic pulverization is 2 to 5; the ball milling time is 60-120 min; the drying time is 2-6 h, and the drying temperature is 80-120 ℃.
24. The method of claim 23, wherein the ball milling time is 60 min.
25. The preparation method according to claim 20, wherein in the step of mixing the resin matrix with the auxiliary agent, the resin matrix is mixed with the photoinitiator, the polymerization initiator and the polymerization inhibitor under stirring, wherein the stirring speed is 3 to 10r/min, and the stirring time is 20 to 40 min.
26. The method according to claim 20, wherein the step of mixing the mixture a with the filler is carried out as follows: adding nano silicon dioxide powder into the mixture A, and stirring and mixing at the stirring speed of 3-10 r/min for 10-20 min; then adding glass powder, stirring and mixing at the stirring speed of 3-10 r/min for 10-20 min to obtain a mixture B.
27. The method according to claim 20, wherein the mixing step of the mixture B with the prepolymerized resin powder comprises, in order: step one, adding the pre-polymerized resin powder into the mixture B, stirring and mixing at a stirring speed of 5-20 r/min for 30-60 min; continuously stirring under the vacuum condition, wherein the stirring speed is 3-10 r/min, and the stirring time is 10-20 min; thirdly, finishing the reaction system under normal pressure, and continuing stirring at the stirring speed of 5-20 r/min for 30-60 min; fourthly, vacuumizing again and stirring continuously, wherein the stirring speed is 5r/min, the vacuum degree is pumped to-0.1 MPa within 5min, and stirring is continuously carried out at the speed of 15-30 r/min under the condition of the vacuum degree of-0.1 MPa for 14-16 min; and fifthly, reversely stirring under a vacuum condition, wherein the stirring speed is 3-10 r/min, the stirring time is 5-10min, and obtaining the tooth filling and repairing material after stirring.
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| KR102444194B1 (en) * | 2020-08-26 | 2022-09-16 | 박성원 | Composition for forming artificial tooth, method of preparing artificial tooth and artificial tooth prepared thereby |
| CN113317995B (en) * | 2021-06-08 | 2022-06-07 | 云南中辉口腔医院有限公司 | Dental restoration material for oral science and preparation method thereof |
| CN113717330B (en) * | 2021-08-26 | 2023-05-05 | 爱迪特（秦皇岛）科技股份有限公司 | Photo-thermal curing resin composition and preparation method and application thereof |
| CN113749950B (en) * | 2021-09-27 | 2023-06-20 | 上海交通大学医学院附属第九人民医院 | Composite resin and preparation method and application thereof |
| CN114478912B (en) * | 2022-01-28 | 2023-09-05 | 上海新世纪齿科材料有限公司 | Photo-curing retention material and application thereof |
| CN114795972A (en) * | 2022-04-12 | 2022-07-29 | 广东工业大学 | Medical enhanced nano composite material and preparation method thereof |
| CN114874396A (en) * | 2022-05-06 | 2022-08-09 | 山东工业陶瓷研究设计院有限公司 | Photosensitive resin for 3D printing and preparation method thereof |
| CN115212117A (en) * | 2022-07-13 | 2022-10-21 | 北京安泰生物医用材料有限公司 | Flowable dental filling resin and preparation method thereof |
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