CN113749950A

CN113749950A - Composite resin and preparation method and application thereof

Info

Publication number: CN113749950A
Application number: CN202111138079.0A
Authority: CN
Inventors: 刘昕; 孙皎; 隋佰延; 郑凯; 陈亚明
Original assignee: Ninth Peoples Hospital Shanghai Jiaotong University School of Medicine
Current assignee: Ninth Peoples Hospital Shanghai Jiaotong University School of Medicine
Priority date: 2021-09-27
Filing date: 2021-09-27
Publication date: 2021-12-07
Anticipated expiration: 2041-09-27
Also published as: CN113749950B

Abstract

The invention provides a composite resin and a preparation method and application thereof. The raw material components of the composite resin comprise bioactive glass microspheres, inorganic filler and resin matrix. The composite resin has good antibacterial performance and can induce tooth tissues to remineralize, and the strength meets the clinical use requirement, so that the composite resin is a good tooth filling material.

Description

Composite resin and preparation method and application thereof

Technical Field

The invention relates to the technical field of medicines, in particular to a composite resin and a preparation method and application thereof.

Background

The caries rate of adults in China is as high as 90 percent, and the effective treatment of caries is the key point and difficulty in the field of oral medicine. In the method, for the affected teeth with moderate or deep caries lesion, cavity filling repair is generally carried out by using filling materials after carious tissues are removed. The composite resin has the advantages of simple and convenient operation, beautiful color, strong operability, good bonding and retention effects and the like, and becomes the most common dental filling material clinically at present. However, studies have shown that the average life of the composite resin filling is only 6 years and the annual failure rate reaches 15%, wherein secondary caries of the composite resin is the most main reason for the failure of the composite resin filling restoration, which is mainly due to the easy accumulation of bacterial plaque on the surface of the composite resin restoration, and the bacterial plaque secretion causes demineralization on the surface of teeth, thereby destroying the tooth structure and providing a passage for the invasion of bacteria. Therefore, how to endow the composite resin with antibacterial performance and remineralization performance so as to effectively reduce the repair failure of the composite resin caused by secondary caries is an important and difficult problem in the research field of the composite resin.

How to reduce secondary caries and actively induce demineralization of tooth tissues is a research hotspot in the field of current tooth filling materials. Currently, much research is focused on improving the inorganic filler, resin matrix and the like of the composite resin: for example, remineralization of a defective portion of a tooth is promoted by adding calcium hydrogen phosphate nanoparticles, tetracalcium phosphate nanoparticles, or calcium fluoride nanoparticles as a nanofiller; the composite resin is endowed with antibacterial performance by introducing antibacterial nanoparticle filler, an antibacterial agent or an antibacterial monomer. However, most of the current approaches for introducing antibacterial performance are to dope antibacterial agents or silver ions, so that the antibacterial performance is rapidly reduced with the time, and the mechanical performance of the composite resin is reduced and the cytotoxicity risk is increased. In addition, most of the current researches are directed to the independent research of antibacterial property or remineralization property of the composite resin, and how to obtain the composite resin with both antibacterial property and remineralization property is rarely reported.

Disclosure of Invention

In view of the above-mentioned disadvantages of the prior art, the present invention aims to provide a composite resin, a preparation method and a use thereof, which is a photo-curing composite resin with antibacterial and remineralizing properties, provides a technical support for reducing the composite resin repair failure caused by secondary caries and tooth tissue demineralization, and is used for solving the problems in the prior art.

To achieve the above objects and other related objects, the present invention is achieved by the following technical solutions.

The invention provides a composite resin, which comprises the raw material components of bioactive glass microspheres, inorganic filler and resin matrix.

Preferably, the inorganic filler includes glass frit and fumed silica nanoparticles.

Preferably, the resin matrix comprises bisphenol a-glycidyl methacrylate (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), a photoinitiator, and ethyl dimethylaminobenzoate.

Preferably, the photoinitiator is Camphorquinone (CQ).

Triethylene glycol dimethacrylate (TEGDMA) is used as a diluent.

Preferably, the preparation method of the bioactive glass microsphere comprises the following steps:

mixing silicon dioxide, calcium carbonate, sodium carbonate and phosphorus pentoxide and sintering to obtain bioactive glass;

then grinding and filtering to obtain the bioactive glass microsphere.

Preferably, a ball mill apparatus is used for milling.

Preferably, the preparation method of the bioactive glass microsphere further comprises the following steps: adding the ground product into an aqueous solution of alkali, heating to form gel, and crushing and filtering the hardened gel.

More preferably, the base is sodium hydroxide. More preferably, the pH of the aqueous solution of the base is 10 to 14. More preferably, the heating temperature for forming the gel by heating is 80-90 ℃.

More preferably, the mass ratio of the silicon dioxide, the calcium carbonate, the sodium carbonate and the phosphorus pentoxide is (10-15): (5-7): (5-10): 1.

more preferably, the sintering temperature is 900-1300 ℃. More preferably, sintering is carried out for 1-4 h at 900-1300 ℃.

More preferably, in the sintering process, the temperature is increased to 900-1300 ℃ firstly, and then sintering is carried out. The heating rate is 400-500 ℃/h.

Preferably, the total mass of the raw material components of the composite resin is taken as a reference, the bioactive glass microspheres are 2 wt% -24 wt%, the resin matrix is 20-30 wt%, and the inorganic filler is 46-78 wt%.

Preferably, the bioactive glass microsphere is 8 wt% to 24 wt%.

Preferably, the bisphenol A-glycidyl methacrylate accounts for 58-65 wt%, the triethylene glycol dimethacrylate accounts for 28-35 wt%, the photoinitiator accounts for 1.5-2.5 wt%, and the ethyl dimethylaminobenzoate accounts for 3.5-4.5 wt% of the total mass of the resin matrix.

Preferably, the surfaces of the bioactive glass microspheres and the glass powder are both subjected to coupling treatment by a silane coupling agent. The silane coupling treatment refers to the prior art, such as contacting and reacting the bioactive glass microspheres and/or the inorganic filler with a silane coupling agent in an organic solvent, respectively. More preferably, the reaction temperature is 50 to 70 ℃.

More preferably, the silane coupling agent is γ -MPS.

Preferably, when the inorganic filler comprises glass powder and fumed silica nanoparticles, the mass ratio of the glass powder to the fumed silica nanoparticles is (15-24): 1.

more preferably, the raw material components of the composite resin comprise 2-24 wt% of bioactive glass microspheres, 49-71 wt% of glass powder, 1-3 wt% of fumed silica nanoparticles and 24 wt% of resin matrix, based on the total mass of the raw material components of the composite resin.

The invention also discloses a preparation method of the composite resin, which comprises the following specific steps:

under the condition of keeping out of the sun, all the components of the resin matrix are mixed to form resin paste, and then the bioactive glass microspheres and the inorganic filler are added and mixed uniformly.

Preferably, the mixing is achieved by centrifugal stirring.

Preferably, the bioactive glass microspheres and the inorganic filler are uniformly mixed and then added into the resin paste.

The invention also discloses the application of the composite resin as a dental filling material.

Preferably, when the composite resin is used for a dental filling material, the composite resin is filled into a defective portion of a dental body and then light-cured.

Preferably, the photo-curing means irradiating with visible light to initiate the curing and crosslinking of the composite resin.

More preferably, the wavelength range of the visible light is 360-520 nm. More preferably, the wavelength range of visible light is 465-470 nm.

The invention also discloses a dental filling material which is obtained by photocuring the composite resin.

The technical scheme of the invention has the beneficial effects that:

(1) the composite resin containing the bioactive glass microspheres can inhibit streptococcus mutans, and the proportion of the number of bacterial colonies is reduced to 32.54-89.96%, which shows that the composite resin has good antibacterial performance;

(2) the composite resin containing the bioactive glass microspheres can induce the demineralized dentin surface to form a lamellar or thicker remineralization layer, almost completely seals dentinal tubules, and the composite resin has good performance of inducing the remineralization of dental tissues;

(3) the bending strength of the composite resin containing the bioactive glass microspheres can reach 103.33-105.41 MPa, is higher than the label specification of ISO4049:2019 dental polymer-based repairing material and YY 1042-2011 dental polymer-based repairing material, and the compression strength is 209.54-232.16 MPa, so that the requirement of clinical application is effectively met.

Drawings

FIG. 1 is a graph showing the results of the direct antibacterial effect of comparative example 1.

FIG. 2 is a graph showing the results of the direct antibacterial effect of example 1.

FIG. 3 is a graph showing the results of the direct antibacterial effect of example 2.

FIG. 4 is a graph showing the results of the direct antibacterial effect of example 3.

FIG. 5 is a graph showing the results of the direct antibacterial effect of example 4.

FIG. 6 is a graph showing the results of the direct antibacterial effect of example 5.

FIG. 7 is a graph showing the results of the direct antibacterial effect of example 5.

FIG. 8 is an SEM photograph of induction of remineralization of demineralized dentin of comparative example 1.

FIG. 9 is an SEM photograph of induction of demineralization of dentin in example 1.

FIG. 10 is an SEM photograph of induction of demineralization of dentin in example 2.

FIG. 11 is an SEM photograph of induction of remineralization of demineralized dentin of example 3.

FIG. 12 is an SEM photograph of induced demineralization of dentin in example 4.

FIG. 13 is an SEM photograph of induction of demineralization of dentin in example 5.

Detailed Description

The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.

Before the present embodiments are further described, it is to be understood that the scope of the invention is not limited to the particular embodiments described below; it is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the respective manufacturers.

When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, and materials used in the examples, any methods, devices, and materials similar or equivalent to those described in the examples may be used in the practice of the invention in addition to the specific methods, devices, and materials used in the examples, in keeping with the knowledge of one skilled in the art and with the description of the invention.

The bioactive glass is a silicate-based biomaterial, consists of oxides such as silicon dioxide, sodium oxide, calcium oxide, phosphorus pentoxide and the like, has high bioactivity, can release ions in a body fluid environment, promotes the formation of a hydroxyapatite layer on the one hand, can increase the pH value of a local environment on the other hand, and provides a foundation for killing bacteria and inducing local mineralization on the two.

The applicant provides a composite resin, and raw material components of the composite resin comprise bioactive glass microspheres, inorganic filler and a resin matrix.

In a preferred embodiment, the inorganic filler comprises glass frit and fumed silica nanoparticles

In a preferred embodiment, the resin matrix comprises bisphenol a-glycidyl methacrylate (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), a photoinitiator, and ethyl dimethylaminobenzoate.

In a preferred embodiment, the photoinitiator is Camphorquinone (CQ).

Triethylene glycol dimethacrylate (TEGDMA) is used as a diluent.

In a preferred embodiment, the method for preparing bioactive glass microspheres comprises:

and then ground. In a preferred embodiment, a ball mill apparatus is used for milling.

In a preferred embodiment, the method for preparing bioactive glass microspheres further comprises: adding the ground product into an aqueous solution of alkali, heating to form gel, and crushing and filtering the hardened gel. In a more preferred embodiment, the base is sodium hydroxide. In a more preferred embodiment, the aqueous solution of the base has a pH of 10 to 14. In a more preferred embodiment, the gel is heated to a temperature of 80 to 90 ℃.

In a preferred embodiment, the particle size of the bioactive glass microspheres is 45-75 μm.

In a preferred embodiment, the particle size of the glass frit is 0.7 to 1 μm.

In a preferred embodiment, the mass ratio of the silicon dioxide, the calcium carbonate, the sodium carbonate and the phosphorus pentoxide is (10-15): (5-7): (5-10): 1.

in a preferred embodiment, the sintering temperature is 900 to 1300 ℃. More preferably, sintering is carried out for 1-4 h at 900-1300 ℃.

In a preferred embodiment, in the sintering process, the temperature is raised to 900-1300 ℃ first, and then sintering is carried out. The heating rate is 400-500 ℃/h.

In a specific embodiment, the bioactive glass is obtained by heating and sintering at 0-400 ℃ for 1 hour (heating rate is 400 ℃/h), heating and sintering at 400-900 ℃ for 1 hour (heating rate is 500 ℃/h), heating and sintering at 900-1300 ℃ for 1 hour (heating rate is 500 ℃/h), and keeping the temperature at 1300 ℃ for 2 hours.

In a preferred embodiment, the content of the bioactive glass microspheres, the content of the resin matrix and the inorganic filler are respectively 2 wt% to 24 wt%, 20 wt% to 30 wt% and 46 wt% to 78 wt%, based on the total mass of the raw material components of the composite resin.

In a preferred embodiment, the bioactive glass microspheres are 8 wt% to 24 wt% by mass.

In a preferred embodiment, the bisphenol A-glycidyl methacrylate is 58 to 65 wt%, the triethylene glycol dimethacrylate is 28 to 35 wt%, the photoinitiator is 1.5 to 2.5 wt%, and the ethyl dimethylaminobenzoate is 3.5 to 4.5 wt%, based on the total mass of the resin matrix.

In a preferred embodiment, the surfaces of the bioactive glass microspheres and the inorganic filler are both subjected to coupling treatment by a silane coupling agent. The silane coupling treatment refers to the prior art, such as contacting and reacting the bioactive glass microspheres and/or the inorganic filler with a silane coupling agent in an organic solvent, respectively. More preferably, the reaction temperature is 50 to 70 ℃.

In a preferred embodiment, the silane coupling agent is γ -MPS.

In a preferred embodiment, when the inorganic filler comprises glass powder and fumed silica nanoparticles, the mass ratio of the glass powder to the fumed silica nanoparticles is (15-24): 1.

in a preferred embodiment, the raw material components of the composite resin comprise 2-24 wt% of bioactive glass microspheres, 49-71 wt% of glass powder, 1-3 wt% of fumed silica nanoparticles and 24 wt% of resin matrix based on the total mass of the raw material components of the composite resin.

In a more preferred embodiment, the content of the bioactive glass microspheres is 8-24 wt%. In a most preferred embodiment, the content of the bioactive glass microspheres is 20-24 wt%.

In a more preferred embodiment, the content of the glass frit is 49 to 65 wt%.

In a more preferred embodiment, the fumed silica nanoparticles can also be present in an amount of 1 wt%, 2 wt%, or 3 wt%.

In a preferred embodiment, the bioactive glass microspheres are first mixed with the inorganic filler uniformly and then added to the resin paste.

In a preferred embodiment, when used as a dental filling material, the composite resin is first filled into a defective portion of a tooth and then light-cured.

In a preferred embodiment, the photo-curing refers to irradiation with visible light to initiate curing and crosslinking of the composite resin. In a more preferred embodiment, the wavelength range of visible light is 360 to 520 nm. In a more preferred embodiment, the visible light has a wavelength in the range of 465 to 470 nm.

The composite resin has good compatibility and reactivity. The product can be used as a filling material for tooth bodies, can effectively inhibit streptococcus mutans and induce remineralization of tooth body tissues, and the strength of the product does not meet the clinical application requirements.

The above technical solutions and the technical effects achieved by the above technical solutions are further explained and explained by specific tests and test effects.

The preparation method of the bioactive glass microspheres used in the following specific experiments was:

weighing 9g of silicon dioxide, 4.8g of calcium carbonate, 4.9g of sodium carbonate and 0.8g of phosphorus pentoxide, shaking and uniformly mixing, and transferring into a crucible for later use; the crucible was transferred into a muffle furnace and sintered according to the following procedure: sintering at 0-400 ℃ for 1 hour (400/DEG C. h)^-1) Sintering at 400-900 ℃ for 1 hour (500/DEG C. h)^-1) Sintering at 900-1300 ℃ for 1 hour (500/DEG C. h)^-1) Keeping the temperature at 1300 ℃ for 2 hours to obtain bioactive glass; grinding by using a grinding instrument; gelling is carried out in 1M NaOH aqueous solution at 85 ℃ for 24 hours with mechanical stirring at 800rpm, and filtering is carried out to obtain the bioactive glass microspheres. The particle size of the bioactive glass microspheres is 45-75 μm.

The procedure for silanization of bioactive glass microspheres and of glass frit in the following specific tests was:

the bioactive glass microspheres and the inorganic filler were added to a cyclohexane solution containing methacryloxypropyltrimethoxysilane (γ -MPS) and stirred at room temperature for 30 minutes. Then stirred at 65 ℃ for 30 minutes. After the reaction is finished, removing the solvent by using a rotary evaporator, washing for 3 times by using absolute ethyl alcohol, and then preparing the silanized bioactive glass microsphere/inorganic filler under the vacuum drying condition.

In the following specific tests, the resin glue solution adopted in the comparative example 1 and the examples 1 to 6 comprises the following raw material components in percentage by weight:

based on the total mass of the resin matrix, the bisphenol A-glycidyl methacrylate accounts for 62.5 wt%, the triethylene glycol dimethacrylate accounts for 31.2 wt%, the photoinitiator accounts for 2.1 wt%, and the ethyl dimethylaminobenzoate accounts for 4.2 wt%.

Comparative example 1

The composite resin in this comparative example did not employ bioactive glass microspheres.

The preparation method comprises the following steps:

uniformly mixing a resin monomer bisphenol A-glycidyl methacrylate and a diluent triethylene glycol dimethacrylate according to the proportion, adding camphorquinone and ethyl dimethylaminobenzoate under strict light-proof conditions, and fully and uniformly stirring to obtain a viscous resin glue solution;

and (3) uniformly mixing 73 wt% of glass powder subjected to surface silane coupling treatment and 3 wt% of fumed silica, sequentially adding the mixture into 24 wt% of viscous resin glue solution, and fully and uniformly stirring in a vacuum stirrer to eliminate bubbles, thereby completing the preparation of the composite resin of the comparative example.

Example 1

uniformly mixing 8 wt% of silane coupling bioactive glass microspheres, 65 wt% of silane coupling glass powder and 3 wt% of fumed silica, sequentially adding the mixture into 24 wt% of viscous resin glue solution, fully and uniformly stirring the mixture in a vacuum stirrer, and eliminating bubbles to obtain the composite resin with antibacterial and remineralizing properties.

Example 2

As described in example 1, except that:

the adding amount of the silane coupling bioactive glass microspheres is 12 wt%, the adding amount of the silane coupling glass powder is 61 wt%, and the adding amount of the fumed silica is 3 wt%, namely the mass ratio of the inorganic filler to the composite resin is kept at 76 wt%.

Example 3

As described in example 1, except that:

the adding amount of the silane coupling bioactive glass microspheres is 16 wt%, the adding amount of the silane coupling glass powder is 57 wt%, and the adding amount of the fumed silica is 3 wt%, namely the mass ratio of the inorganic filler to the composite resin is kept at 76 wt%.

Example 4

As described in example 1, except that:

the adding amount of the silane coupling bioactive glass microspheres is 20 wt%, the adding amount of the silane coupling glass powder is 53 wt%, and the adding amount of the fumed silica is 3 wt%, namely the mass ratio of the inorganic filler to the composite resin is kept at 76 wt%.

Example 5

As described in example 1, except that:

the adding amount of the silane coupling bioactive glass microspheres is 24 wt%, the adding amount of the silane coupling glass powder is 49 wt%, and the adding amount of the fumed silica is 3 wt%, namely the mass ratio of the inorganic filler to the composite resin is kept at 76 wt%.

Example 6

As described in example 1, except that:

the adding amount of the silane coupling bioactive glass microspheres is 2 wt%, the adding amount of the silane coupling glass powder is 71 wt%, and the adding amount of the fumed silica is 3 wt%, namely the mass ratio of the inorganic filler to the composite resin is kept at 76 wt%.

Comparative example 2

As described in example 1, except that:

the adding amount of the silane coupling bioactive glass microspheres is 28 wt%, the adding amount of the silane coupling glass powder is 45 wt%, and the adding amount of the fumed silica is 3 wt%, namely the mass ratio of the inorganic filler to the composite resin is kept at 76 wt%.

Comparative example 3

As shown in example 1, except that: bioactive glass microspheres which are not silanized are adopted.

Comparative example 4

As shown in example 1, except that:

the resin glue solution comprises the following raw material components in percentage by weight: the weight percentage of the bisphenol A-glycidyl methacrylate is 55 percent, the weight percentage of the triethylene glycol dimethacrylate is 38.7 percent, the weight percentage of the photoinitiator is 2.1 percent, and the weight percentage of the ethyl dimethylaminobenzoate is 4.2 percent.

Comparative example 5

As shown in example 1, except that:

the resin glue solution comprises the following raw material components in percentage by weight: based on the total mass of the resin matrix, the bisphenol A-glycidyl methacrylate accounts for 68 wt%, the triethylene glycol dimethacrylate accounts for 25.7 wt%, the photoinitiator accounts for 2.1 wt%, and the ethyl dimethylaminobenzoate accounts for 4.2 wt%.

Test example 1

And (3) detecting the bacteriostatic effect of the comparative example 1 and the examples 1-5 by using a direct contact method.

The composite resins of comparative examples 1 to 2 and examples 1 to 5 were used to prepare cylindrical samples (n: 3) having a diameter of 6mm and a height of 4mm, and the cylindrical samples were sterilized for use. 0.2mL of Streptococcus mutans (1X 10) per well of the cell culture plate was added⁵CFU/mL)2mL of BHI culture medium, and respectively contacting the samples with the composite resin samples of the comparative example and the examples 1-5, carrying out anaerobic incubation at 37 ℃ for 24h, taking out the samples, completely eluting bacteria adhered to the surfaces of the samples, carrying out gradient dilution on the eluent, inoculating 100 mu L of diluent to a BHI agar plate, taking a picture, and carrying out colony counting and analysis by using Image-J software.

FIGS. 1 to 7 are direct antibacterial effect diagrams of comparative example 1 and examples 1 to 6, respectively, in this order.

The colony inhibition amounts and inhibition ratios of comparative example 1 and examples 1 to 6 are shown in Table 1.

TABLE 1

	Number of colonies (number)	Inhibition ratio (%)
			Comparative example 1	1178.67±7.50	/
Example 1	795.15±6.28	32.54±2.15
			Example 2	748.33±7.37	36.51±2.71
Example 3	416.33±9.24	64.68±4.87
			Example 4	266.16±8.21	77.42±4.26
Example 5	181.33±1.58	89.96±0.37
			Example 6	1166.78±9.24	1.06±0.59

^*P < 0.05vs. comparative example 1

The results of the antibacterial effect of the comparative example 1 and the examples 1 to 6 are combined to prove that the introduction of the bioactive glass microspheres with lower content (2 wt%) can not obviously inhibit the colony number (P is more than 0.05) (figures 1 to 7, table 1); when the content of the bioactive glass microspheres is 8-24 wt%, the composite resin can obviously reduce the number of bacterial colonies of streptococcus mutans (P is less than 0.05), the antibacterial proportion of the composite resin is improved, the antibacterial effect of the composite resin is gradually improved along with the increase of the content of the bioactive glass microspheres, and the concentration dependence relationship is provided, so that the introduction of the bioactive glass microspheres with proper mass fraction can effectively improve the antibacterial performance of the composite resin.

Test example 2

Demineralization tests of comparative example 1 and examples 1-5.

Sample wafers of 6mm in diameter and 4mm in thickness were prepared for use in comparative examples and examples 1 to 5, respectively.

Selecting the first premolar to be pulled out due to orthodontics, embedding and fixing by using epoxy resin, and horizontally cutting into tooth slices with the thickness of 1mm below the cementum enamel boundary of each tooth by using a hard tissue microtome. The above-mentioned dental sections were washed with 0.5% sodium hypochlorite for 5 minutes, then washed alternately with distilled water and 70% alcohol, and then immersed in a 10% phosphoric acid solution for 12 hours for demineralization. The tooth slices after demineralization were immersed in Simulated Body Fluid (SBF) with the comparative examples and sample discs of examples 1 to 5, respectively [ SBF addition amounts of each group were calculated according to the formula Vs Sa/10, wherein Vs SPF addition volume (mL) and Sa immersion sample surface area (mm)²) In the experimental groups, after being continuously soaked in SBF at 37 ℃ for 21 days, samples are taken out at normal temperatureDrying, and observing the remineralization condition of the dental sections by using a scanning electron microscope.

FIGS. 8 to 13 are SEM images of induced demineralization of dentin in comparative example 1 and examples 1 to 5, respectively, in this order.

The results of examples 1-5 induced remineralization of demineralized dentin (FIGS. 9-13) show: after the demineralized dentin sheet is contacted with a comparative example, dentin tubules are clearly visible, and apatite crystal deposition is not seen; after the demineralized dentin sheets are respectively contacted with the embodiments 1-5, partial mineralized deposition can be seen on the surfaces of all groups of dentin, wherein after the demineralized dentin sheets are respectively contacted with the embodiments 4 and 5, a large amount of mineralized immersion particles on the surfaces of dentin are seen to be fused into sheets, mineralized layers are gradually cleared away, and even dentin tubules are completely sealed, which shows that the remineralization performance of the composite resin can be effectively improved by the bioactive glass microspheres.

Test example 3

Measurement of mechanical Properties of comparative examples 1 to 4 and examples 1 to 5

According to ISO4049: the comparative examples and examples 1 to 5 were as follows, as required by 2020: a standard test piece (n-5) was made in a size of 25mm × 2mm × 2mm in length (l) × height (h) × width (b). After the test piece is completely cured, detecting the bending strength of the test piece by using a universal mechanical testing machine, and setting experimental parameters: the span (L) was 20mm, the loading rate was 0.5mm/min until the test piece broke, and the maximum load pmax (n) at break was recorded. Bending strength (S) according to the formula: s (mpa) ═ 3PmaxL/(2 bh)²) The flexural strength of comparative examples and examples 1 to 5 was calculated.

According to ISO4049: 2020, the comparative examples and examples 1 to 5 were prepared into cylindrical test pieces (n: 5) having a diameter of 4mm and a height of 6 mm. After the test piece is completely cured, clamping the test piece on a universal material testing machine, and carrying out a compression strength test, wherein the loading speed of a loading head is 1mm/min, recording the breaking load F when the test piece is broken, and the Compression Strength (CS) is according to the formula: CS (MPa) ═ F/π r²The compressive strengths of comparative examples and examples 1 to 5 were calculated.

The flexural strength and compressive strength results for comparative examples 1-4 and examples 1-5 are shown in Table 2.

TABLE 2

The result shows that the silanization-treated bioactive glass microspheres containing the appropriate proportion (8-24 wt%) can be effectively and uniformly dispersed in the composite resin, and the clinical requirements on the mechanical property of the composite resin are guaranteed through self-silanization. When the proportion of the bioactive glass microspheres which are not subjected to silanization treatment or are subjected to silanization treatment is too high, the bioactive glass microspheres cannot be effectively dispersed in an organic matrix of the composite resin, so that the bending strength and the compression strength of the composite resin are remarkably reduced and are lower than 80MPa required by the standard. In addition, comparative examples 4 to 5 also show that when the proportion of the resin glue solution is adjusted, the mechanical property of the composite resin is reduced, and the requirements of clinical application are not met.

Note: ISO4049 2019 dental polymer-based restorative material and YY 1042 and 2011 dental polymer-based restorative material are marked to specify that the flexural strength of the polymer-based filling and restorative material suitable for occlusal restoration should not be lower than 80 MPa.

The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.

Claims

1. The composite resin is characterized in that raw material components of the composite resin comprise bioactive glass microspheres, inorganic filler and resin matrix.

2. The composite resin according to claim 1, wherein the inorganic filler is selected from one or both of glass frit and fumed silica nanoparticles; and/or the resin matrix comprises bisphenol A-glycidyl methacrylate, triethylene glycol dimethacrylate, a photoinitiator and ethyl dimethylaminobenzoate.

3. The composite resin according to claim 2, wherein when the inorganic filler comprises glass frit and fumed silica nanoparticles, the mass ratio of the glass frit to the fumed silica nanoparticles is (15-24): 1.

4. the composite resin of claim 3, wherein the photoinitiator is camphorquinone;

and/or, based on the total mass of the resin matrix, the bisphenol A-glycidyl methacrylate accounts for 58-65 wt%, the triethylene glycol dimethacrylate accounts for 28-35 wt%, the photoinitiator accounts for 1.5-2.5 wt%, and the ethyl dimethylaminobenzoate accounts for 3.5-4.5 wt%.

5. The composite resin as claimed in claim 1 or 2, wherein the bioactive glass microspheres are 2-24 wt%, the resin matrix is 20-30 wt%, and the inorganic filler is 46-78 wt%;

and/or, the bioactive glass microsphere is obtained by a preparation method comprising the following steps: mixing silicon dioxide, calcium carbonate, sodium carbonate and phosphorus pentoxide and sintering to obtain bioactive glass; then grinding and filtering to obtain the bioactive glass microspheres;

and/or the surfaces of the bioactive glass microspheres and the glass powder are subjected to coupling treatment by a silane coupling agent.

6. The composite resin according to claim 5, wherein the mass ratio of the silica to the calcium carbonate to the sodium carbonate to the phosphorus pentoxide is (10-15): (5-7): (5-10): 1; and/or the sintering temperature is 900-1300 ℃.

7. The composite resin of claim 2, wherein the raw material components of the composite resin comprise 2-24 wt% of bioactive glass microspheres, 49-71 wt% of glass powder, 1-3 wt% of fumed silica nanoparticles and 24 wt% of resin matrix, based on the total mass of the raw material components of the composite resin.

8. A method for preparing the composite resin as claimed in any one of claims 1 to 7, comprising: under the condition of keeping out of the sun, all the components of the resin matrix are mixed to form resin paste, and then the bioactive glass microspheres and the inorganic filler are added and mixed uniformly.

9. Use of the composite resin according to any one of claims 1 to 7 as a dental filling material.

10. A dental filling material, which is obtained by photocuring the composite resin according to any one of claims 1 to 7.