CN109481317A

CN109481317A - A kind of gear division reparation nanocomposite and preparation method thereof

Info

Publication number: CN109481317A
Application number: CN201710813675.1A
Authority: CN
Inventors: 王洁欣; 杨丹蕾; 王丹; 陈建峰
Original assignee: Beijing University of Chemical Technology
Current assignee: Beijing University of Chemical Technology
Priority date: 2017-09-11
Filing date: 2017-09-11
Publication date: 2019-03-19

Abstract

The invention discloses a nanocomposite resin for dental restoration, comprising a resin matrix, a photoinitiator and modified inorganic nanoparticles and/or nanoparticle clusters; and also discloses a preparation method of the nanocomposite resin for dental restoration. The nano-composite resin for dental restoration of the present invention can keep the surface smooth after the resin matrix is worn, and the composite resin exhibits good mechanical properties; the preparation method of the present invention uses inorganic nanoparticles and/or nano-particle clusters as The filler can uniformly fill nanoparticles and/or nanoparticle clusters in the resin matrix; the method is simple and has wide applicability; the nanoparticles and/or nanoparticle clusters are monodispersed in the resin matrix; the obtained tooth In the nanocomposite resin for repairing, the organic and inorganic components have good compatibility.

Description

A kind of gear division reparation nanocomposite and preparation method thereof

Technical field

The invention belongs to the preparation field of gear division repair materials, more particularly, to a kind of gear division reparation with nano combined tree Rouge and preparation method thereof.

Background technique

Dental caries are one of oral cavity common diseases, in recent years, gear division reparation resin composite materials because its performance attractive in appearance is excellent, The advantages that clinical manipulation is simple and efficient and tooth caking property is good, toxicity stimulation is few, gradually replaces silver amalgam, it has also become state Inside and outside main, most popular dental caries filling renovation material.But such material at present there are still some shortcomings, receive by such as polymerization The problems such as shrinkage height, mechanical property and tooth body mismatch and wearability is poor in the long-term use, these deficiency limitations Such material is more widely applied.

Composite dental restoration resin is mainly made of resinous substrates, inorganic filler and photoinitiator system, wherein inorganic Filler is the deciding factor of compound resin physical property and mechanical performance.Inorganic filler is dispersed in resin system, Neng Goufu The good physicochemical property of composite material is given, while there are also reduce the cubical contraction of composite material, supplement mineral, increase antibiotic property The properties such as energy.In numerous inorganic fillers, the mechanical performances such as rigidity, intensity are can be enhanced in silica；Zirconium oxide energy The X-ray resistance for enough improving compound resin, has high intensity, high rigidity, high optical transparency；Zinc oxide and titanium dioxide energy Compound resin tensile strength and impact strength are enough improved, while improving the antibiotic property of compound resin；Hydroxyapatite can supplement Mineral promotes remineralization, while improving its mechanical property.

Pattern, partial size and the packed structures of inorganic filler are to the physical-mechanical property of material, especially mechanical property and resistance to Mill property has a major impact.The inorganic filler original adoption of composite dental restoration resin be partial size is 10-50 μm of bulky grain Type filler, inorganic particle filled amount is higher in such compound resin, and mechanical property is preferable, but can lead after resinous substrates fall off Cause filler expose, and the filler fall off after easily form biggish pit in resin surface, influence the polishability and beauty of compound resin See performance.Composite dental restoration resin uses partial size as the microparticle type filler of 40-50nm later, such resin finish Property it is preferable, but since the particle diameter is smaller, large specific surface area so that in corresponding compound resin inorganic filler filling Measure that lower, wearability is poor.In addition, nano particle filling mode is all made of powder filling at this stage, it is dried in nano particle During powder, inevitably reunite.When as applying filler, nano particle will lead in resinous substrates In be unevenly distributed, influence the mechanical performance of compound resin.Requirement with patient to resin for restoration comprehensive performance, it is suitable to have both The micro- filler of the mixing of mechanical strength and performance attractive in appearance is used in compound resin.Such filler ion is by 10-50 μm of bulky grain The nanoparticle of about 40nm forms, so that the content of inorganic filler increases to 75-80wt%.But in clinic is on active service, such The polishing retentivity and wear-resisting property of material be not good enough.

It wears no resistance to solve micron filler loading height in dental repair resin simultaneously and nanofiller is wear-resisting Property is good and contradiction that load capacity is low, and a kind of nanoparticle cluster filler comes into being, such filler is by state of aggregation nanoparticle The common micro-scaled filler of composition can assign resin material excellent comprehensive performance.3M company [1] is once using the method preparation of calcining Nanoparticle cluster body (Mohammad Atai, Ayoub Pahlavan, Niloofar Moin.Nano-porous thermally sintered nano silica as novel fillers for dental composites[J] .Dental Materials, 2012,28:133-145.), this method is by dispersed nano SiO₂And/or ZrO₂Colloidal sol is through high temperature Nanocluster is obtained after calcining and grinding, particle diameter distribution is mostly from nanoscale to micron order.But this method is needed nanoparticle Son is sintered at 1300 DEG C, and energy consumption is high, and product pattern and controllability are poor.Ruili Wang et al. [2] is once using coupling Method prepare Nano particles of silicon dioxide cluster body (Ruili Wang, Shuang Bao, Fengwei Liu, et al.Wear behavior of light-cured resin composites with bimodal silica nanostructures As fillers [J] .Materials Science and Engineering C, 2013,33:4759-4766.), this method By a part of silicon dioxide granule amino functional, it is coupled after another part is Epoxy functionalized, is made in this way again Standby nanoparticle cluster body technology is complicated, time-consuming, and the pattern and partial size of cluster body are uncontrollable, it cannot be guaranteed that silica nanometer The monodisperse of particle, and be merely able to it is single use silica for filler, the advantage for playing each inorganic filler cannot be integrated.

Since nanoparticle cluster body is common micro-scaled filler, when being filled in resinous substrates as filler, cluster body Between have larger gap, influence loading of the inorganic filler in compound resin.In order to solve this problem, Ruili Wang Et al. [2] et al. nanoparticle and nanocluster body are filled in resinous substrates according to a certain percentage, obtained total filler amount For 70% resin composite materials.But it uses the method that powder is directly filled, and makes nanoparticle and nanoparticle cluster body It is distributed not uniform enough.

Therefore, it is necessary first to provide a kind of simple process, low energy consumption, and preparation time is short, and adaptability to raw materials is wide, product cut size Controllably, pattern and all more uniform method for preparing monodisperse nanoparticle cluster body of partial size；Secondly, it is desirable to provide Yi Zhonggong Skill is simple, and nanoparticle and nanoparticle cluster body can be uniformly filled in the fill method of resinous substrates.

Summary of the invention

The invention solves first technical problem be to provide a kind of gear division reparation nanocomposite.The gear division is repaired It is multiplexed nanocomposite, after resinous substrates abrasion, the smooth of surface can be kept.And compound resin shows good machine Tool performance.

The invention solves second technical problem be to provide the preparation side of gear division reparation nanocomposite a kind of Method.This method, can be by nanoparticle and/or nanoparticle group using inorganic nano-particle and/or nanoparticle cluster body as filler Cluster body is uniformly filled in resinous substrates；Method is simple, and applicability is wide；Realize that nanoparticle and/or nanoparticle cluster body are equal The monodisperse in resinous substrates；In obtained gear division reparation nanocomposite, organic and inorganic component compatibility is good.

In order to solve the first technical problem mentioned above, the present invention adopts the following technical scheme that:

A kind of gear division reparation nanocomposite, including resinous substrates, photoinitiator and modified inorganic nano-particle And/or nanoparticle cluster body.That is, resinous substrates, photoinitiator be must raw material, modified inorganic nano-particle and/ Or nanoparticle cluster body both is to select one, or both all to include.

In some embodiments of the present invention, the resinous substrates include that main monomer bisphenol-A-Glycidyl methacrylate is sweet Grease (referred to as: Bis-GMA) further includes auxiliary monomer triethylene glycol and methacrylate (referred to as: TEGDMA), carbamate One of double methyl methacrylate (referred to as: UDMA).

In some embodiments of the present invention, the resinous substrates account for the 20-95wt.% of nanocomposite.

In some embodiments of the present invention, the photoinitiator includes main initiator camphorquinone (referred to as: CQ) and helps Initiator 4- dimethyl ethyl aminobenzoate (referred to as: 4-EDMAB)；The quality of photoinitiator accounts for the 1-2wt.% of resinous substrates, The mass ratio of main initiator and aided initiating is 1:2-1:6.

In some embodiments of the present invention, the modified inorganic nano-particle includes improved silica nanoparticle Son, modified zirconia nanoparticle, modified zinc oxide nanoparticle, modified titanium dioxide nano particle, modified hydroxylapatite One of nanoparticle, modified fluorinated calcium nanoparticle, modified phosphate calcium nanoparticle are a variety of.

In some embodiments of the present invention, the nanocluster body includes Nano particles of silicon dioxide cluster body, oxygen Change zirconium nanoparticle cluster body, zinc oxide nano-particle cluster body, titanium dioxide nano-particle cluster body, hydroxyapatite nano One of Compound Clusters body that particle cluster body, modified inorganic nano-particle are formed is a variety of；The nanoparticle cluster body Assemble the cluster body structure for uniform, the fine and close arrangement to be formed for modified inorganic nano-particle, partial size is 1-10 μm.

In some embodiments of the present invention, modified inorganic nano-particle and/or nanometer in the nanocomposite Particle cluster body accounts for 5-80wt.%；Modified inorganic nano-particle can be mixed with nanoparticle cluster body with arbitrary proportion.

To solve above-mentioned second technical problem, a kind of above-mentioned preparation side of gear division reparation nanocomposite of the present invention Method includes the following steps:

S1, resinous substrates, photoinitiator and modified inorganic nano-particle dispersion and/or nanoparticle cluster body are mixed It closes, mixed process is filled using solution blended process or powder filling:

The filling of S1-1 solution blended process

Modified inorganic nano-particle dispersion is carried out rotary evaporation by S1-1-1, improves the solid content of dispersion；Raising changes The purpose of property inorganic nano-particle molecular dispersion solid content is, so that modified inorganic nano-particle dispersion is blended with resinous substrates After uniformly, solvent can be easier to volatilize complete；

S1-1-2 presses the modified inorganic nano-particle dispersion after rotary evaporation, nanoparticle cluster body, resinous substrates Ratio is uniformly mixed, and obtains the mixing containing modified inorganic nano-particle, nanoparticle cluster body, decentralized medium and resinous substrates Object；After solvent is volatilized, photoinitiator is added into mixture and is further uniformly mixed, obtains uncured resin cream A；

The filling of S1-2 powder

Modified inorganic nano-particle dispersion is put into vacuum freeze drier and is freeze-dried by S1-2-1, obtains nothing Machine nanoparticle powder；It is using the method purpose of vacuum freeze drying: reduces the group in inorganic nano-particle drying process Poly- phenomenon；

S1-2-2 mixes inorganic nano-particle powder, nanoparticle cluster body, photoinitiator and resinous substrates in proportion Uniformly, uncured resin cream B is obtained；

S2, gear division reparation is obtained with nano combined tree after uncured resin cream A or uncured resin cream B is carried out photocuring Rouge；

In some embodiments of the present invention, the preparation method of the modified inorganic nano-particle molecular dispersion is such as Under: modifying agent is added into inorganic nanodispersion and is modified, obtains modified Nanodispersion；Inorganic nanodispersion Including inorganic nano-particle and decentralized medium；Modified purpose is: so that nanoparticle is well dispersed in the medium, Bu Huifa Raw precipitating, if some inorganic particles cannot stable dispersion in the medium without modification；In addition, the table of inorganic nanoparticles The modified compatibility that nanoparticle (inorganic) Yu resinous substrates (organic) interface can be improved in face, with reach higher amount of filler and Superior performance；

In some of the preferred embodiment of the invention, the inorganic nano-particle includes Nano particles of silicon dioxide, oxygen Change zirconium nanoparticle, zinc oxide nano-particle, titanium dioxide nano-particle, hydroxyapatite nano particle, calcirm-fluoride nanoparticle One of son, calcium phosphate nano particle are a variety of.

As the preferred embodiment of the present invention, the inorganic nano-particle pattern is spherical shape, nanometer rods, cube and eight One of face body is a variety of.

In some of the preferred embodiment of the invention, the decentralized medium is selected from methanol, ethyl alcohol, methylene chloride, tetrahydro One of furans, chloroform, acetone, hexamethylene, n-hexane, water are a variety of.

In some of the preferred embodiment of the invention, the modifying agent is selected from gamma-aminopropyl-triethoxy-silane (letter Claim: KH550), γ-glycidyl ether oxygen propyl trimethoxy silicane (referred to as: KH560), γ-methacryloxypropyl three Methoxy silane (referred to as: KH570), γ-glycidyl ether oxygen propyl trimethoxy silicane (referred to as: GPTMS), 3- aminopropyl three Ethoxysilane (referred to as: APTES), 3- isocyanide propyl-triethoxysilicane (referred to as: IPTES), polyethylene glycol (referred to as: PEG) One of or it is a variety of.

In some of the preferred embodiment of the invention, the mass ratio of the inorganic nano-particle and modifying agent is 100:1- 100:50.For example, it is also possible to be 100:1-100:45 or 100:1-100:40 or 100:1-100:35 or 100:1-100: 30 or 100:1-100:25 or 100:1-100:20 or 100:1-100:15 or 100:1-100:10 or 100:1-100:5, Or 100:3-100:50 or 100:3-100:45 or 100:3-100:40 or 100:3-100:35 or 100:3-100:30, or 100:3-100:25 or 100:3-100:20 or 100:3-100:15 or 100:3-100:10.

In some of the preferred embodiment of the invention, modification temperature is 20-100 DEG C.For example, it is also possible to be 20-90 DEG C, Or 20-80 DEG C or 20-70 DEG C or 20-60 DEG C or 20-50 DEG C or 20-40 DEG C or 20-30 DEG C or 30-100 DEG C or 30- 90 DEG C or 30-80 DEG C or 30-70 DEG C or 30-60 DEG C or 30-50 DEG C or 30-40 DEG C or 40-100 DEG C or 40-90 DEG C, Or 40-80 DEG C or 40-70 DEG C or 40-60 DEG C or 40-50 DEG C or 50-100 DEG C or 50-90 DEG C or 50-80 DEG C or 50- 70 DEG C or 50-60 DEG C or 60-100 DEG C or 60-90 DEG C or 60-80 DEG C or 60-70 DEG C or 70-100 DEG C or 70-90 DEG C, Or 70-80 DEG C or 80-100 DEG C or 80-90 DEG C.

In some of the preferred embodiment of the invention, modification time 1-20h.For example, it is also possible to be 1-18h or 1- 16h or 1-14h or 1-12h or 1-10h or 1-8h or 1-6h or 1-4h or 1-2h or 3-20h or 3-18h or 3- 16h or 3-14h or 3-12h or 3-10h or 3-8h or 3-6h or 6-20h or 6-18h or 6-16h or 6-14h, or 6-12h or 6-10h or 6-8h or 10-20h or 10-18h or 10-16h or 10-14h or 10-12h or 12-20h, or 12-18h or 12-16h or 12-14h.

In some embodiments of the present invention, the preparation method of the nanoparticle cluster body, steps are as follows: will be above-mentioned Resulting modified inorganic nanodispersion, which is passed through in spray dryer, to be spray-dried, and nanoparticle cluster body is obtained.

As the preferred embodiment of the present invention, the solid content of the modified inorganic nanodispersion of spray-drying feedstock For 1-10%；Preferably 2-5%.

As the preferred embodiment of the present invention, dispersion input speed is 0.05-0.5L/ in the spray-drying process H, preferably 0.2-0.4L/h.

As the preferred embodiment of the present invention, compressed air pressure is 0.1-0.4MPa in the spray-drying process, Select 0.3-0.4MPa.

As the preferred embodiment of the present invention, temperature is 90-120 DEG C at nozzle in the spray-drying process.

In some embodiments of the present invention, in step S1-1-1, the temperature of the rotary evaporation is 20 DEG C -70 DEG C.

As the preferred embodiment of the present invention, in step S1-1-1, inorganic nanodispersion after the rotary evaporation Solid content is 5-50%, preferably 10-30%.

As the preferred embodiment of the present invention, in step S1-1-2 and S1-2-2, solvent volatilization and resinous substrates and nothing The method that machine nanoparticle and/or nanocluster body and photoinitiator further mix is to iterate through three-roller.

As the preferred embodiment of the present invention, in step S2, the wavelength that photocuring is used up is 430-490nm.

As the preferred embodiment of the present invention, in step S2, the time of photocuring is 60-120s.

Any range documented by the present invention includes any numerical value between end value and end value and end value or end value Between any subrange for being constituted of any number.

Unless otherwise specified, each raw material in the present invention can be obtained by commercially available purchase, equipment used in the present invention The conventional equipment in fields can be used or carried out referring to the prior art of fields.

Compared with prior art, the invention has the following beneficial effects:

1) method of present invention preparation gear division reparation nanocomposite is simple, and adaptability to raw materials is wide, and nanoparticle exists During forming cluster body, all nanoparticles can all form cluster body, and particle diameter distribution is narrow, pattern is uniform, cluster body particle It is≤70% spherical in shape, at low cost, method is simple, preparation process continuity is good, is suitble to large-scale production.

2) using the method for nanoparticle cluster body is prepared in the present invention, a variety of nanoparticles may be implemented collectively as receiving The raw material of rice corpuscles cluster body, and every kind of nanoparticle can uniformly, be densely arranged in entire cluster structure.

3) method of the invention is used, the preferable nanoparticle cluster body of monodispersity can be prepared, is convenient for nanoparticle Dispersion of the sub- cluster body in resin matrix.

4) using the present invention in prepare gear division reparation nanocomposite method, can by inorganic nanoparticles and/ Or nanoparticle cluster body is uniformly filled in resinous substrates.

It 5), can be common by a variety of nanoparticles using the method for preparing gear division reparation nanocomposite in the present invention It is filled in resinous substrates, plays the advantage in each inorganic nanoparticles performance.

6) the gear division reparation nanocomposite prepared using method of the invention can after resinous substrates abrasion To keep the smooth of surface.

7) good mechanical performance is shown with nanocomposite using the gear division reparation that method of the invention is prepared.

Detailed description of the invention

Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing

Fig. 1 is the SEM figure of gained compound resin section in embodiment 1.

Fig. 2 is the SEM figure of gained compound resin section in embodiment 2.

Fig. 3 is scanning electron microscope (SEM) figure of freeze-drying gained nano silica powder in embodiment 4.

Fig. 4 is the SEM figure of gained compound resin section in embodiment 4.

Fig. 5 is that the SEM figure that nanometer titanium dioxide silicon clusters body is made is spray-dried in embodiment 6.

Fig. 6 is that the grain size distribution that nanometer titanium dioxide silicon clusters body is made is spray-dried in embodiment 6.

The SEM figure of gained compound resin section in Fig. 7 embodiment 6.

Fig. 8 is that the SEM figure that nanometer titanium dioxide silicon clusters body is made is spray-dried in embodiment 7.

Fig. 9 is that the SEM figure that nano zine oxide cluster body is made is spray-dried in embodiment 7.

Figure 10 is that the SEM figure that nano silica-zinc oxide Compound Clusters body is made is spray-dried in embodiment 8.

Figure 11 is that the grain size distribution that nano silica-zinc oxide Compound Clusters body is made is spray-dried in embodiment 8.

Figure 12 is that EDS points that silica-zirconia composite nanoparticle cluster body is made are spray-dried in embodiment 8 Analysis.

Figure 13 is the SEM figure of commercially available SiO 2 powder filling gained compound resin section in comparative example 5.

Specific embodiment

In order to illustrate more clearly of the present invention, below with reference to preferred embodiment, the present invention is described further.Ability Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this The protection scope of invention.

Method of evaluating performance in the present invention is as follows:

1) three-point bending strength and bending modulus

Uncured resin cream is inserted in 25mm × 2mm × 2mm mold, is solidified upper and lower surface respectively with light-solidified lamp 60s, the batten after being solidified are stored under 37 DEG C of constant temperature after demoulding.It is drawn off polishing and being tested afterwards for 24 hours, survey Its three-point bending strength and bending modulus, every group of 6 samples.

2) compressive strength

By in the mold of uncured resin cream filling Φ 4mm × 6mm, its upper and lower surface is solidified respectively with light-solidified lamp 60s, after demoulding after be stored under 37 DEG C of constant temperature.It is drawn off polishing and carrying out compressive strength test, every group of 6 samples afterwards for 24 hours.

3) hardness

By in the mold of uncured resin cream filling Φ 4mm × 6mm, its upper and lower surface is solidified respectively with light-solidified lamp 60s, after demoulding after be stored under 37 DEG C of constant temperature.It is drawn off polishing and carrying out hardness test afterwards for 24 hours, takes 5 on each sample A point is tested.

Embodiment 1

A kind of preparation method of gear division reparation nanocomposite

The present embodiment is filled using the Nano particles of silicon dioxide of partial size 40nm as raw material using solution blended process, and tooth is prepared Section repairs and uses resin composite materials.The following steps are included:

Step 1: the modification of inorganic nano-particle:

The modification of nano silica: taking 200mL solid content is 5% silica nanometer dispersion, two in dispersion The partial size of silica is 40nm, and decentralized medium is the mixed liquor of water and ethyl alcohol；0.1mL KH570 is added thereto, it is high at room temperature After speed stirring 30min, 65 DEG C are warming up to, continues to stir 30min, obtains modified manometer silicon dioxide dispersion；

Step 2: the raising of Nanodispersion solid content:

The water-bath of Rotary Evaporators is adjusted to 40 DEG C, step 1 gained modified manometer silicon dioxide dispersion is revolved Turn evaporation, obtains the Nano silicon dioxide dispersion that solid content is 12%；

Step 3: the preparation of gear division reparation nanocomposite:

Table 1 is the component of compound resin and the content of each component

Component	Mass fraction (wt.%)
		Bis-GMA	24.75
TEGDMA	24.75
		CQ	0.1
4-EDMAB	0.4
		Silica	50

By table 1 by the dispersion of the modified manometer silicon dioxide particle containing corrresponding quality and resinous substrates (Bis-GMA and TEGDMA it) is uniformly mixed, iterates through three-roller, after solvent volatilization completely, photoinitiator (CQ and 4- are added thereto EDMAB), it is uniformly mixed further again by three-roller, obtain uncured resin cream；Gear division is obtained after photocuring to repair It is multiplexed nanocomposite.

Through detecting, gained compound resin three-point bending strength is 104MPa, bending modulus 4.1GPa, and compressive strength is 315MPa, hardness 21HV.

Fig. 1 is compound resin cross-section morphology figure, it can be seen from the figure that nanoparticle is evenly distributed in resinous substrates, Section keeps smooth.

Embodiment 2

A kind of preparation method of gear division reparation nanocomposite

The present embodiment is original with the titanium dioxide nano-particle of the Nano particles of silicon dioxide of partial size 50nm and partial size 20nm Material, is filled using solution blended process, prepares gear division reparation resin composite materials.The following steps are included:

Step 1: the modification of inorganic nano-particle:

The modification of nano silica: taking 100mL solid content is 8% silica nanometer dispersion, two in dispersion The partial size of silica is 50nm, and decentralized medium is the mixed liquor of water and ethyl alcohol；1.5mL KH550 is added thereto, it is high at room temperature After speed stirring 30min, 65 DEG C are warming up to, continues to stir 30min, obtains modified manometer silicon dioxide dispersion；

The modification of nano-titanium dioxide: taking 100mL solid content is 3% nano titania dispersion, and decentralized medium is Water；The partial size of titanium dioxide is 20nm；0.3mL KH550 is added into dispersion, is put into water heating kettle the hydro-thermal at 160 DEG C 4h is centrifuged after reaction, washs three times, disperses in 100mL ethyl alcohol, obtain modified nano-titanium dioxide dispersion；

Step 2: the raising of Nanodispersion solid content:

The temperature of Rotary Evaporators is adjusted to 40 DEG C, respectively to step 1 gained modified manometer silicon dioxide dispersion and changing Property nano-titanium dioxide dispersion carry out rotary evaporation, obtain modified manometer silicon dioxide dispersion that solid content is 10% and solid The modified nano-titanium dioxide dispersion that content is 5%.

Step 3: the preparation of gear division reparation nanocomposite:

Table 2 is the component of compound resin and the content of each component:

Component	Mass fraction (wt.%)
		Bis-GMA	22.27
TEGDMA	22.27
		CQ	0.1
4-EDMAB	0.36
		Silica	50
Titanium dioxide	5

By table 2 by the dispersion containing corrresponding quality modified manometer silicon dioxide particle and modified nano-titanium dioxide particle Resinous substrates (Bis-GMA and TEGDMA) is added thereto and iterates through three rollers after mixing by mixing, magnetic agitation 3min Machine completely to solvent volatilization is added photoinitiator (CQ and 4-EDMAB) thereto, mixes it further again by three-roller It closes uniformly, obtains uncured resin cream.Gear division reparation nanocomposite is obtained after photocuring.

Through detecting, gained compound resin three-point bending strength is 106MPa, bending modulus 4.4GPa, and compressive strength is 322MPa, hardness 27HV.

Fig. 2 is compound resin cross-section morphology figure, it can be seen from the figure that nanoparticle is evenly distributed in resinous substrates, Section keeps smooth.

Embodiment 3

A kind of preparation method of gear division reparation nanocomposite

The present embodiment is with the Nano particles of silicon dioxide of partial size 80nm, the hydroxyapatite and partial size 10nm that draw ratio is 20 Zinc oxide nano-particle be raw material, filled using solution blended process, prepare gear division reparation resin composite materials.Including following Step:

Step 1: the modification of inorganic nano-particle:

The modification of nano silica: taking 100mL solid content is 5% silica nanometer dispersion, two in dispersion The partial size of silica is 80nm, and decentralized medium is the mixed liquor of water and ethyl alcohol；1mL KH560 is added thereto, at room temperature high speed After stirring 30min, 70 DEG C are warming up to, continues to stir 30min, obtains modified manometer silicon dioxide dispersion；

The modification of nanometer hydroxyapatite: preparing the Aqueous Solutions of Polyethylene Glycol that 100mL concentration is 6%, and slurries nanometer is added In hydroxyapatite, ultrasonic vibration 30min, 40 DEG C are stirred at reflux 4h, continue to heat magnetic agitation 2h, three times with water centrifuge washing After be scattered in ethyl alcohol, be made 100mL solid content be 2% modifted-nano-hydroxyapatite dispersion；

The modification of nano zine oxide: taking 100mL solid content is 3% nano zine oxide ethyl alcohol phase suspension, zinc oxide Partial size is 10nm, and 0.5mL KH560 is added thereto at room temperature, and warming while stirring continues to stir to 60 DEG C after temperature is constant 30min is dispersed in water with dehydrated alcohol centrifuge washing three times to get modified nano zinc oxide dispersion；

Step 2: the raising of Nanodispersion solid content:

The temperature of Rotary Evaporators is adjusted to 40 DEG C, respectively to modified manometer silicon dioxide dispersion and modified Nano hydroxyl Apatite dispersion carries out rotary evaporation, obtains modified manometer silicon dioxide dispersion that solid content is 10% and solid content is 5% modifted-nano-hydroxyapatite dispersion.The temperature of Rotary Evaporators is adjusted to 70 DEG C, modified nano zinc oxide is dispersed Body carries out rotary evaporation, obtains the modified nano zinc oxide dispersion that solid content is 10%；

Step 3: the preparation of gear division reparation nanocomposite:

Table 3 is the component of compound resin and the content of each component:

Corrresponding quality modified manometer silicon dioxide particle, modifted-nano-hydroxyapatite particle and modification will be contained by table 3 The dispersion of nano zinc oxide particles mixes, and resinous substrates are added thereto, after mixing, lead to repeatedly by magnetic agitation 5min Three-roller is crossed, completely to solvent volatilization, photoinitiator is added thereto, is uniformly mixed it further again by three-roller, Obtain uncured resin cream；Gear division reparation nanocomposite is obtained after photocuring.

Through detecting, gained compound resin three-point bending strength is 108MPa, bending modulus 4.8GPa, and compressive strength is 330MPa, hardness 35HV.

Embodiment 4

A kind of preparation method of gear division reparation nanocomposite

The present embodiment using the zirconium oxide nano-particle of the Nano particles of silicon dioxide of partial size 40nm and partial size 40nm as raw material, The method filled using powder prepares gear division reparation resin composite materials.The following steps are included:

Step 1: the modification of inorganic nano-particle:

The modification of nano silica: taking 100mL solid content is 5% silica nanometer dispersion, two in dispersion The partial size of silica is 40nm, and decentralized medium is hexamethylene；1mL KH570 is added thereto, at room temperature high-speed stirred 30min Afterwards, 70 DEG C are warming up to, continues to stir 30min, obtains modified manometer silicon dioxide dispersion.

The modification of nano zircite: taking 100mL solid content is 3% nano zircite benzyl alcohol phase suspension, zirconium oxide Partial size be 5nm；Three times with tetrahydrofuran centrifuge washing, it disperses the zirconium oxide being centrifuged in containing 0.5mL KH570's In 100mL toluene, it is stirred at room temperature after 30min and is warming up to 60 DEG C and continues to stir 12h；It is centrifuged out precipitating after reaction, is dispersed in In hexamethylene, modified nano zircite dispersion is obtained；

Step 2: the preparation of nano-powder:

Nano silicon dioxide dispersion and nano zircite dispersion are put into freeze drier and are freeze-dried, is obtained To nano silica and nano zirconium oxide powder；

Step 3: the preparation of gear division reparation nanocomposite:

Table 4 is the component of compound resin and the content of each component:

Component	Mass fraction (wt.%)
		Bis-GMA	17.3
TEGDMA	17.3
		CQ	0.08
4-EDMAB	0.32
		Silica	60
Zirconium oxide	5

The modified manometer silicon dioxide particle, modified Nano Zirconia particles and resinous substrates of corrresponding quality are mixed by table 4 It closes, premix is infiltrated by resinous substrates to inorganic powder manually, and photoinitiator is then added thereto, keeps it mixed by three-roller It closes uniformly, obtains uncured resin cream.Gear division reparation nanocomposite is obtained after photocuring.

Through detecting, gained compound resin three-point bending strength is 120MPa, bending modulus 6.2GPa, and compressive strength is 372MPa, hardness 50HV.

Fig. 3 is the SEM figure of freeze-drying gained nano silica in step 2.

Fig. 4 is compound resin cross-section morphology figure, it can be seen from the figure that nanoparticle is evenly distributed in resinous substrates, Section keeps smooth.

Embodiment 5

A kind of preparation method of gear division reparation nanocomposite

The present embodiment is with the Nano particles of silicon dioxide of partial size 100nm, the zirconium oxide nano-particle of partial size 10nm, partial size The nanometer hydroxyapatite that the zinc oxide nano-particle of 20nm, draw ratio are 10 is raw material, the method filled using powder, preparation Gear division reparation resin composite materials.The following steps are included:

Step 1: the modification of inorganic nano-particle:

The modification of nano silica: taking 100mL solid content is 5% silica nanometer dispersion, two in dispersion The partial size of silica is 40nm, and decentralized medium is methanol；0.5mL GPTMS is added thereto, stirs 1h at 60 DEG C, is changed Property Nano silicon dioxide dispersion.

The modification of nano zircite: taking 100mL solid content is 2% nano zircite benzyl alcohol phase suspension, zirconium oxide Partial size be 10nm；Three times with ethyl alcohol centrifuge washing, it disperses the zirconium oxide being centrifuged in containing 0.5mL GPTMS's In 100mL tetrahydrofuran, 1h is stirred at room temperature, obtains modified Nano zirconia dispersion.

The modification of nano zine oxide: taking 100mL solid content is 3% nano zine oxide ethyl alcohol phase suspension, zinc oxide Partial size is 20nm, and 0.5mL GPTMS is added thereto at room temperature, and warming while stirring continues to stir to 60 DEG C after temperature is constant 30min is dispersed in water with dehydrated alcohol centrifuge washing three times to get modified nano zinc oxide dispersion.

The modification of nanometer hydroxyapatite: take 1mL GPTMS that the slurries nano hydroxyapatite that 100mL solid content is 5% is added In lime stone, ultrasonic vibration 30min, 40 DEG C are stirred at reflux 4h, continue to heat magnetic agitation 2h, be dispersed afterwards three times with water centrifuge washing Yu Shuizhong obtains modifted-nano-hydroxyapatite dispersion.

Step 2: the preparation of nano-powder:

Modified nano silica, zirconium oxide, zinc oxide, hydroxyapatite dispersion are put into freeze drier It is freeze-dried, obtains corresponding powder.

Step 3: the preparation of gear division reparation nanocomposite:

Table 5 is the component of compound resin and the content of each component:

Component	Mass fraction (wt.%)
		Bis-GMA	17.3
TEGDMA	17.3
		CQ	0.08
4-EDMAB	0.32
		Silica	50
Zirconium oxide	5
		Zinc oxide	5
Hydroxyapatite	5

According to the ratio in table 5 by resinous substrates, photoinitiator, nano silica, zirconium oxide, zinc oxide, hydroxyl phosphorus It premixes after the mixing of lime stone powder, after inorganic filler is sufficiently infiltrated by resinous substrates, is further mixed it by three-roller manually It closes uniformly, obtains uncured resin cream.Gear division reparation nanocomposite is obtained after photocuring.

Through detecting, gained compound resin three-point bending strength is 119MPa, bending modulus 6GPa, and compressive strength is 355MPa, hardness 55HV.

Embodiment 6

A kind of preparation method of gear division reparation nanocomposite

The present embodiment prepares nanometer two using the Nano particles of silicon dioxide of partial size 40nm as raw material, using spray drying technology Silicon clusters body is aoxidized, and by it as filler, gear division reparation resin composite materials are prepared using the method for powder filling.Including Following steps:

Step 1: the modification of inorganic nano-particle:

The modification of nano silica: taking 200mL solid content is 5% silica nanometer dispersion, two in dispersion The partial size of silica is 40nm, and decentralized medium is the mixed liquor of water and ethyl alcohol；1mL APTES is added thereto, at room temperature high speed After stirring 30min, 65 DEG C are warming up to, continues to stir 30min, obtains modified manometer silicon dioxide dispersion；

Step 2: the preparation of nanoparticle cluster body:

Modified manometer silicon dioxide dispersion is passed through in spray dryer with peristaltic pump and is spray-dried；Spray drying The technological parameter of use are as follows: Nano silicon dioxide dispersion input speed is 0.3L/h；Compressed air pressure is 0.2MPa；Nozzle Locating temperature is 100 DEG C；

Step 3: the preparation of gear division reparation nanocomposite:

Table 6 is the component of compound resin and the content of each component

It is premixed manually after mixing resinous substrates, photoinitiator and nanometer titanium dioxide silicon clusters body according to the ratio in table 6, After inorganic filler is sufficiently infiltrated by resinous substrates, it is further uniformly mixed by three-roller, obtains uncured resin cream. Gear division reparation nanocomposite is obtained after photocuring.

Through detecting, gained compound resin three-point bending strength is 110MPa, bending modulus 5.1GPa, and compressive strength is 332MPa, hardness 25HV.

It is illustrated in figure 5 nanoparticle cluster body shape appearance figure.Nanoparticle cluster body is spherical in shape, and partial size is 1-3 μm, nanometer Particle cluster body monodispersity in resinous substrates is 100%；

It is illustrated in figure 6 nanoparticle cluster body grain size distribution.

It is illustrated in figure 7 nanocomposite cross-section diagram, it can be seen that section is smooth, and nanometer titanium dioxide silicon clusters body is equal It is even to be distributed in resinous substrates.

Embodiment 7

A kind of preparation method of gear division reparation nanocomposite

The present embodiment is using the zinc oxide of the silica of partial size 80nm and partial size 15nm as raw material, using spray drying technology Nanometer titanium dioxide silicon clusters body and nano zine oxide cluster body are prepared respectively, it is prepared into gear division reparation resin as filler Composite material.The following steps are included:

Step 1: the modification of inorganic nano-particle:

The modification of nano silica: taking 100mL solid content is 5% silica nanometer dispersion, two in dispersion The partial size of silica is 80nm, and decentralized medium is water；0.5mL KH570 is added thereto, at room temperature after high-speed stirred 30min, 65 DEG C are warming up to, continues to stir 30min, obtains modified manometer silicon dioxide dispersion.

The modification of nano zine oxide: taking 100mL solid content is 3% nano zine oxide ethyl alcohol phase suspension, zinc oxide Partial size is 15nm, and 0.3mL KH570 is added thereto at room temperature, and warming while stirring continues to stir to 60 DEG C after temperature is constant 30min is dispersed in water with dehydrated alcohol centrifuge washing three times to get modified nano zinc oxide dispersion.

Step 2: the preparation of nanoparticle cluster body:

Modified manometer silicon dioxide dispersion and modified nano zinc oxide dispersion are passed through with peristaltic pump and are done by spraying respectively It is spray-dried in dry machine；It is equal to be spray-dried the technological parameter used are as follows: dispersion input speed is 0.4L/h；Compressed air Pressure is 0.3MPa；Temperature is 120 DEG C at nozzle.

Step 3: the preparation of gear division reparation nanocomposite:

Table 7 is the component of compound resin and the content of each component

Component	Mass fraction (wt.%)
		Bis-GMA	14.85
TEGDMA	14.85
		CQ	0.06
4-EDMAB	0.24
		Silica (cluster body)	60
Zinc oxide (cluster body)	10

According to the ratio in table 6 by resinous substrates, photoinitiator, nanometer titanium dioxide silicon clusters body, nano zine oxide cluster It premixes after body mixing, after inorganic filler is sufficiently infiltrated by resinous substrates, is further uniformly mixed it by three-roller manually, Obtain uncured resin cream.Gear division reparation nanocomposite is obtained after photocuring.

Through detecting, gained compound resin three-point bending strength is 118MPa, bending modulus 5.5GPa, and compressive strength is 320MPa, hardness 52HV.

It is as shown in Figure 8, Figure 9 respectively nanometer titanium dioxide silicon clusters body and nano zine oxide cluster body shape appearance figure.It can by figure To find out, nanoparticle arrangement is neat and fine and close in nanocluster body.

Embodiment 8

A kind of preparation method of gear division reparation nanocomposite

The present embodiment is using the zinc oxide of the silica of partial size 40nm and partial size 20nm as raw material, using spray drying technology Nano silica-zinc oxide Compound Clusters body is prepared, it is prepared into gear division reparation resin composite materials as filler.Packet Include following steps:

Step 1: the modification of inorganic nano-particle:

The modification of nano silica: taking 100mL solid content is 5% Nano silicon dioxide dispersion, two in dispersion The partial size of silica is 50nm, and decentralized medium is the mixed liquor of water and ethyl alcohol；0.5mL IPTES is added thereto, it is high at room temperature After speed stirring 30min, 65 DEG C are warming up to, continues to stir 30min, obtains modified manometer silicon dioxide dispersion；

The modification of nano zine oxide: taking 100mL solid content is 1% nano zine oxide ethyl alcohol phase suspension, zinc oxide Partial size is 20nm, and 0.1mL IPTES is added thereto at room temperature, and warming while stirring continues to stir to 60 DEG C after temperature is constant 30min is dispersed in water with dehydrated alcohol centrifuge washing three times to get modified nano zinc oxide dispersion；

Step 2: the preparation of nanoparticle cluster body:

Under room temperature, nano oxidized zinc dispersion obtained in step 1 is added to nano silica dispersion while stirring In body, ultrasonic disperse 10min obtains silica-zirconia hybrid dispersions.It is passed through in spray dryer with peristaltic pump It is spray-dried；It is spray-dried the technological parameter used are as follows: hybrid dispersions input speed is 0.4L/h；Compressed air pressure For 0.3MPa；Temperature is 150 DEG C at nozzle；

Step 3: the preparation of gear division reparation nanocomposite:

Table 8 is the component of compound resin and the content of each component

Component	Mass fraction (wt.%)
		Bis-GMA	19.8
TEGDMA	19.8
		CQ	0.1
4-EDMAB	0.3
		Silica & zinc oxide (cluster body)	60

Resinous substrates, photoinitiator and nano silica-zinc oxide cluster body are mixed into defensive position according to the ratio in table 8 It, after inorganic filler is sufficiently soaked by resinous substrates, is further uniformly mixed by three-roller, is obtained uncured by dynamic premix Resin plaster.Gear division reparation nanocomposite is obtained after photocuring；

Through detecting, gained compound resin three-point bending strength is 115MPa, bending modulus 5.2GPa, and compressive strength is 328MPa, hardness 38HV；

It is as shown in Figure 10 nano silica-zinc oxide cluster body shape appearance figure.Nanoparticle cluster body 70% is spherical in shape, Nanoparticle cluster body monodispersity in resinous substrates is 100%, and partial size is 1-5 μm；

Figure 11 is cluster body grain size distribution；

Figure 12 show cluster body EDS analysis result.

Embodiment 9

A kind of preparation method of gear division reparation nanocomposite

Calcirm-fluoride nanoparticle of the present embodiment with the Nano particles of silicon dioxide of partial size 40nm, partial size for 15nm is former Material mixes, using solution blending after preparing nano calcium fluoride cluster body using spray drying process with Nano particles of silicon dioxide Mode is filled, and gear division reparation resin composite materials are prepared.The following steps are included:

Step 1: the modification of inorganic nano-particle:

The modification of nano silica: taking 100mL solid content is 3% silica nanometer dispersion, two in dispersion The partial size of silica is 40nm, and decentralized medium is ethyl alcohol；0.6mL KH550 is added thereto, at room temperature high-speed stirred 30min Afterwards, 70 DEG C are warming up to, continues to stir 30min, obtains modified manometer silicon dioxide dispersion；

The modification of nano calcium fluoride: preparing the Aqueous Solutions of Polyethylene Glycol that 100mL concentration is 6%, and the fluorination of slurries nanometer is added In calcium, ultrasonic vibration 30min, 40 DEG C are stirred at reflux 4h, continue to heat magnetic agitation 2h, are scattered in afterwards three times with water centrifuge washing In ethyl alcohol, the modified Nano calcirm-fluoride dispersion that 100mL solid content is 2% is made；

Step 2: the raising of Nanodispersion solid content:

The water-bath of Rotary Evaporators is adjusted to 40 degrees Celsius, rotation steaming is carried out to modified manometer silicon dioxide dispersion Hair obtains the modified manometer silicon dioxide dispersion that solid content is 12%.

Step 3: the preparation of nanoparticle cluster body:

Modified Nano calcirm-fluoride dispersion is passed through in spray dryer with peristaltic pump and is spray-dried；Spray drying is adopted Technological parameter are as follows: dispersion input speed is 0.5L/h；Compressed air pressure is 0.3MPa；Temperature is 130 DEG C at nozzle.

Step 4: the preparation of gear division reparation nanocomposite:

Table 9 is the component of compound resin and the content of each component

Component	Mass fraction (wt.%)
		Bis-GMA	17.3
TEGDMA	17.3
		CQ	0.08
4-EDMAB	0.32
		Silica	45
Calcirm-fluoride (cluster body)	20

Nano calcium fluoride cluster body is added in modified manometer silicon dioxide dispersion according to the ratio in table 9, magnetic force stirs Mixing 5min is uniformly mixed it, and resinous substrates are added thereto, continues after stirring 2min, mixed liquor is iterated through three-roller, After solvent volatilization completely, photoinitiator is added thereto, is uniformly mixed it further again by three-roller, obtains not solid Change resin plaster.Gear division reparation nanocomposite is obtained after photocuring；

Through detecting, gained compound resin three-point bending strength is 117MPa, bending modulus 5.2GPa, and compressive strength is 345MPa, hardness 45HV.

Embodiment 10

A kind of preparation method of gear division reparation nanocomposite

The present embodiment is with the Nano particles of silicon dioxide of partial size 40nm, the titanium dioxide nano-particle of partial size 20nm, partial size The zirconium oxide nano-particle of 10nm be raw material, nanometer titanium dioxide silicon clusters body is prepared using the method for spray drying, later with it is cold Freeze titanium dioxide, the zirconium oxide nano-particle being dried to obtain to fill jointly, prepares gear division reparation resin composite materials.Including with Lower step:

Step 1: the modification of inorganic nano-particle:

The modification of nano silica: taking 100mL solid content is 3% silica nanometer dispersion, two in dispersion The partial size of silica is 40nm, and decentralized medium is acetone；0.3mL APTES is added thereto, at room temperature high-speed stirred 30min Afterwards, 70 DEG C are warming up to, continues to stir 30min, obtains modified manometer silicon dioxide dispersion；

The modification of nano zircite: taking 100mL solid content is 2% nano zircite benzyl alcohol phase suspension, zirconium oxide Partial size be 5nm；Three times with ethyl alcohol centrifuge washing, the 100mL containing 0.2mL APTES is dispersed by the zirconium oxide being centrifuged In tetrahydrofuran, 60min is stirred at room temperature, obtains modified Nano zirconia dispersion；

The modification of nano-titanium dioxide: taking 100mL solid content is 3% nano-titanium dioxide aqueous dispersion, titanium dioxide Partial size be 20nm；0.3mL KH550 is added into dispersion, is put into water heating kettle the hydro-thermal 4h at 160 DEG C, obtains modification and receives Rice titanium dioxide dispersion.

Step 2: the preparation of nanoparticle cluster body:

Modified manometer silicon dioxide dispersion is passed through in spray dryer with peristaltic pump and is spray-dried；Spray drying The technological parameter of use are as follows: dispersion input speed is 0.3L/h；Compressed air pressure is 0.3MPa；Temperature is 100 at nozzle ℃。

Step 3: the preparation of nano-powder:

Modified Nano zirconia dispersion and modified nano-titanium dioxide dispersion are put into freeze drier carry out it is cold It is lyophilized dry, obtains corresponding powder.

Step 4: the preparation of gear division reparation nanocomposite:

Table 10 is the component of compound resin and the content of each component

Component	Mass fraction (wt.%)
		Bis-GMA	17.3
TEGDMA	17.3
		CQ	0.08
4-EDMAB	0.32
		Silica (cluster body)	50
Zirconium oxide	10
		Titanium dioxide	5

According to the ratio in table 10 by resinous substrates, photoinitiator, nanometer titanium dioxide silicon clusters body, nano oxidized zirconium powder It is premixed manually after body, nano-titanium dioxide powder mixing, it, will by three-roller after inorganic filler is sufficiently soaked by resinous substrates It is further uniformly mixed, and obtains uncured resin cream.Gear division reparation nanocomposite is obtained after photocuring.

Through detecting, gained compound resin three-point bending strength is 125MPa, bending modulus 6.8GPa, and compressive strength is 344MPa, hardness 61HV.

Comparative example 1

Compared with the product disclosed in by the patent No. 201110000350.4, filler distribution figure compares in resin, this The product inorganic nanoparticles of embodiment are distributed more uniform in resin, and section is more smooth.

Comparative example 2

With by the patent No. 201210525631.6 disclosed in compared with product, prepared nanocluster body in the present embodiment Method is simpler, and the cluster body monodispersity prepared is more preferable, and compound resin section is more compared with its cross-section diagram, in the present embodiment Add smooth.

Comparative example 3

Compared with the product disclosed in by the patent No. 201310676816.1, compressive strength is whole in the product of the present embodiment Body improves 50% or more.

Comparative example 4

Compared with the product disclosed in by the patent No. 201310042561.3, the inorganic filler ratio filled in resinous substrates Example is higher, and cost is lower.Compared with its cross-section diagram, the product inorganic nanoparticles dispersibility of the present embodiment is more preferable, in resin It is distributed more uniform, section is more smooth.

Comparative example 5

Solution blended process filling and modified commercially available nano grade silica particles filling gained compound resin are compared, it is curved Qu Qiangdu and compressive strength respectively improve 10%, and commercially available SiO 2 powder filling gained compound resin cross-section diagram is as shown in figure 13, As Fig. 1 and Fig. 3 comparison as can be seen that more using inorganic nano-filler distribution in compound resin obtained by solution blended process filling Uniformly, section is more smooth.

Comparative example 6

The filling of nanocluster body and modified commercially available nano grade silica particles filling gained compound resin are compared, it is curved Qu Qiangdu and compressive strength respectively improve 15%, and comparison diagram 7 and Figure 13 can be seen that nanocluster body and fill more uniform, section It is more smooth.

Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description To make other variations or changes in different ways.Here all embodiments can not be exhaustive.It is all to belong to this hair The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.

Claims

1. A nanocomposite resin for dental restoration, characterized in that: comprising a resin matrix, a photoinitiator and modified inorganic nanoparticles and/or nanoparticle clusters.

2. The nanocomposite resin for dental restoration according to claim 1, wherein the resin matrix comprises the main monomer bisphenol A-glycidyl methacrylate, and also comprises the auxiliary monomers triethylene glycol and methyl methacrylate. One of base acrylate and urethane dimethacrylate; the resin matrix accounts for 20-95 wt.% of the nanocomposite resin.

3. The nanocomposite resin for dental restoration according to claim 1, wherein the photoinitiator comprises a main initiator camphorquinone and a co-initiator ethyl 4-dimethylaminobenzoate; the quality of the photoinitiator It accounts for 1-2wt.% of the resin matrix, and the mass ratio of the main initiator and the co-initiator is 1:2-1:6.

4. The nanocomposite resin for dental restoration according to claim 1, wherein the modified inorganic nanoparticles comprise modified silica nanoparticles, modified zirconia nanoparticles, modified zinc oxide nanoparticles, One or more of modified titanium dioxide nanoparticles, modified hydroxyapatite nanoparticles, modified calcium fluoride nanoparticles, and modified calcium phosphate nanoparticles;

The nano-clusters include silica nano-particle clusters, zirconia nano-particle clusters, zinc oxide nano-particle clusters, titanium dioxide nano-particle clusters, hydroxyapatite nano-particle clusters, modified One or more of the composite clusters formed by the modified inorganic nanoparticles; the nanoparticle clusters are uniform and densely arranged cluster structures formed by the aggregation of modified inorganic nanoparticles, with a particle size of 1- 10μm.

5. The nanocomposite resin for dental restoration according to claim 1, characterized in that: in the nanocomposite resin, modified inorganic nanoparticles and/or nanoparticle clusters account for 5-80 wt.%; Particles and nanoparticle clusters can be mixed in any ratio.

6. the preparation method of the nanocomposite resin for dental restoration as described in any one of claim 1-5, is characterized in that, comprises the steps:

S1. Mix the resin matrix, the photoinitiator, and the modified inorganic nanoparticle dispersion and/or nanoparticle cluster. The mixing process is filled by solution blending or powder filling:

S1-1 solution blending method filling

S1-1-1 performs rotary evaporation of the modified inorganic nanoparticle dispersion to increase the solid content of the dispersion;

S1-1-2 Mix the modified inorganic nanoparticle dispersion, nanoparticle cluster and resin matrix after rotary evaporation uniformly in proportion to obtain modified inorganic nanoparticles, nanoparticle cluster, dispersion medium and resin matrix After the solvent is volatilized, a photoinitiator is added to the mixture and further mixed to obtain uncured resin paste A;

S1-2 powder filling

S1-2-1 Put the modified inorganic nanoparticle dispersion into a vacuum freeze dryer for freeze drying to obtain inorganic nanoparticle powder;

S1-2-2 Mix the inorganic nanoparticle powder, nanoparticle cluster, photoinitiator and resin matrix uniformly in proportion to obtain uncured resin paste B;

S2. After photocuring the uncured resin paste A or the uncured resin paste B, a nanocomposite resin for dental restoration is obtained.

7. The preparation method of the nanocomposite resin for dental restoration according to claim 6, wherein the preparation method of the modified inorganic nanoparticle dispersion is as follows: adding a modifier to the inorganic nanodispersion for modification , to obtain a modified nano-dispersion; the inorganic nano-dispersion includes inorganic nanoparticles and a dispersion medium.

8 . The preparation method of nanocomposite resin for dental restoration according to claim 7 , wherein the inorganic nanoparticles comprise silica nanoparticles, zirconia nanoparticles, zinc oxide nanoparticles, titanium dioxide nanoparticles, hydroxyl One or more of apatite nanoparticles, calcium fluoride nanoparticles, and calcium phosphate nanoparticles;

Preferably, the morphology of the inorganic nanoparticles is one or more of spherical, nanorod, cube and octahedron;

Preferably, the dispersion medium is selected from one or more of methanol, ethanol, dichloromethane, tetrahydrofuran, chloroform, acetone, cyclohexane, n-hexane, and water;

Preferably, the modifier is selected from the group consisting of γ-aminopropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ- - one or more of glycidyl ether oxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-isocyanopropyltriethoxysilane, and polyethylene glycol;

Preferably, the mass ratio of the inorganic nanoparticles to the modifier is 100:1-100:50, or 100:1-100:45, or 100:1-100:40, or 100:1-100:35 , or 100:1-100:30, or 100:1-100:25, or 100:1-100:20, or 100:1-100:15, or 100:1-100:10, or 100:1 -100:5, or 100:3-100:50, or 100:3-100:45, or 100:3-100:40, or 100:3-100:35, or 100:3-100:30, or 100:3-100:25, or 100:3-100:20, or 100:3-100:15, or 100:3-100:10;

Preferably, the modification temperature is 20-100°C, or 20-90°C, or 20-80°C, or 20-70°C, or 20-60°C, or 20-50°C, or 20-40°C, or 20°C -30℃, or 30-100℃, or 30-90℃, or 30-80℃, or 30-70℃, or 30-60℃, or 30-50℃, or 30-40℃, or 40-100 ℃, or 40-90℃, or 40-80℃, or 40-70℃, or 40-60℃, or 40-50℃, or 50-100℃, or 50-90℃, or 50-80℃, or 50-70°C, or 50-60°C, or 60-100°C, or 60-90°C, or 60-80°C, or 60-70°C, or 70-100°C, or 70-90°C, or 70°C -80℃, or 80-100℃, or 80-90℃.

Preferably, the modification time is 1-20h, or 1-18h, or 1-16h, or 1-14h, or 1-12h, or 1-10h, or 1-8h, or 1-6h, or 1-4h , or 1-2h, or 3-20h, or 3-18h, or 3-16h, or 3-14h, or 3-12h, or 3-10h, or 3-8h, or 3-6h, or 6-20h , or 6-18h, or 6-16h, or 6-14h, or 6-12h, or 6-10h, or 6-8h, or 10-20h, or 10-18h, or 10-16h, or 10-14h , or 10-12h, or 12-20h, or 12-18h, or 12-16h, or 12-14h.

9 . The preparation method of nanocomposite resin for dental restoration according to claim 6 , wherein the preparation method of the nanoparticle clusters comprises the following steps: passing the modified inorganic nanodispersion into a spray dryer. 10 . spray-drying to obtain nanoparticle clusters;

The solid content of the inorganic nano-dispersion after modification of the spray-dried raw material is 1-10%; preferably 2-5%;

Preferably, the input speed of the dispersion in the spray drying process is 0.05-0.5 L/h; more preferably 0.2-0.4 L/h;

Preferably, the compressed air pressure in the spray drying process is 0.1-0.4MPa; more preferably, 0.3-0.4MPa;

Preferably, the temperature at the nozzle during the spray drying process is 90-120°C.

10. The preparation method of nanocomposite resin for dental restoration according to claim 6, wherein in step S1-1-1, the temperature of the rotary evaporation is 20°C-70°C;

Preferably, in step S1-1-1, the solid content of the inorganic nano-dispersion after rotary evaporation is 5-50%, preferably 10-30%;

Preferably, in steps S1-1-2 and S1-2-2, the solvent is volatilized and the resin matrix is further mixed with inorganic nanoparticles and/or nanoclusters and photoinitiators by repeatedly passing through a three-roller machine;

Preferably, in step S2, the wavelength of light used for photocuring is 430-490 nm;

Preferably, in step S2, the light curing time is 60-120s.