CN107117962A - A kind of preparation method of the dental all-ceramics repair materials based on electrostatic self-assembled technology - Google Patents

A kind of preparation method of the dental all-ceramics repair materials based on electrostatic self-assembled technology Download PDF

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CN107117962A
CN107117962A CN201710307668.4A CN201710307668A CN107117962A CN 107117962 A CN107117962 A CN 107117962A CN 201710307668 A CN201710307668 A CN 201710307668A CN 107117962 A CN107117962 A CN 107117962A
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CN107117962B (en
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王衍根
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Zhongshan Ruifeng Medical Devices Co., Ltd.
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Zhengzhou Han Technology Co Ltd
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Abstract

The present invention relates to a kind of preparation method of the dental all-ceramics repair materials based on electrostatic self-assembled technology, belong to dental material technical field.The key technology of use is to make one layer of titanium oxide sol particle of Surface coating of zirconia material by the method for electrostatic self-assembled, by the overlap joint of titanium oxide sol in sintering process, the problem of material for solving thermal coefficient of expansion difference between zirconium oxide and other aggregates and bringing is easy to crack.

Description

A kind of preparation method of the dental all-ceramics repair materials based on electrostatic self-assembled technology
Technical field
The present invention relates to a kind of preparation method of the dental all-ceramics repair materials based on electrostatic self-assembled technology, belong to dentistry Field of material technology.
Background technology
Dental polishing repair volume morphing color and luster with it is naturally similar, using when seem nature, true to nature, depth is welcome by patient.Ceramics are repaiied Complex quality is fine and close, wear-resisting, any surface finish, and bacterial plaque is difficult attachment, has good biocompatibility, uses safety.Therefore, it is ceramic It is the material of commonly used making artificial tooth.Oral cavity ceramics are the most stable of materials of chemical property in oral cavity material, be can tolerate The effect of many chemical substances is without changing, for a long time under the conditions of oral environment, to various foods, beverage, saliva, body The effect of liquid, microorganism and its enzyme, will not produce rotten, denaturation.Oral cavity ceramic material has preferable biology performance, in mouth Intracavitary uses safe and nontoxic.
At present, its material mainly used is zirconium oxide, and it has good biocompatibility, corrosion resistance, stability high Advantage, zirconia content is more than 50%, and its flexural strength is improved with the increase of zirconia content.High intensity aluminium porcelain is mainly used Make the primer of composite ceramic hat.Preparation method is usually to be injected after zirconia ceramics material is melted in mold, then is cooled to Precast body, then the porcelain by crystallization processing, precipitation crystalline phase within specified temperatures, make material obtain sufficient intensity.Through Cross the ceramic material referred to as cast ceramic material cast after crystallization processing.It is many at present to be cast using glass ceramics, Its casting technique typically uses investment casting or for lost wax process.
Oral cavity ceramic material is heat insulation body, and coefficient of thermal expansion is approached with tooth body.But oral cavity ceramic material makes in sintering During, there is larger volume contraction and influence the precision of dummy.
The content of the invention
The purpose of the present invention is：The fragility height of dental all-ceramics repair materials presence is solved, processes and is easily opened in working angles The problem of splitting；The present invention proposes a kind of preparation method of the dental all-ceramics repair materials based on electrostatic self-assembled technology, uses Key technology be to make one layer of titanium oxide sol particle of Surface coating of zirconia material by the method for electrostatic self-assembled, pass through The overlap joint of titanium oxide sol in sintering process, the material for solving thermal coefficient of expansion difference between zirconium oxide and other aggregates and bringing The problem of expecting easy to crack.
Technical scheme is：
A kind of preparation method of the dental all-ceramics repair materials based on electrostatic self-assembled technology, comprises the following steps：
1st step, the pretreatment of powder：Take ZrO2Powder, SnO2Powder, is dispersed in water respectively, and solid content is configured to respectively and is Slurry is filtered out after 10~15% slurry, ball milling, after spray drying, the ZrO after ball milling is respectively obtained2、SnO2Powder；
2nd step, the preparation of the ionic liquid of silane coupler grafting：In alcohols solvent, 2~4wt% silane coupler is added Glyoxaline ion liquid with 6~8%, reacts after 12~16h at 85~90 DEG C, obtains the ionic liquid of silane coupler grafting The solution of body；
3rd step, ZrO2The surface cationic of powder：By the ZrO after ball milling2Powder is immersed in the ion of silane coupler grafting Handled in the solution of liquid, obtain the ZrO of surface cationic2Powder；
4th step, the preparation of the titanium oxide sol of negative electrical charge：By weight, by 30~45 parts of butyl titanate, sodium sulphate 10 ~12 parts well mixed with 350~450 parts of water, after heating, and sulfuric acid solution is added dropwise to the pH of system 4~5, is hydrolyzed anti- Should；It is cooled to after room temperature, adds 20~25 parts of hydroxy silicon oil, be modified reaction, reaction solution is concentrated under reduced pressure into volume for it Preceding 40~50%, add NaOH solution regulation pH to 9~11, obtain the titanium oxide sol of surface negative charge；
5th step, the surface electrostatic self assembly of Zirconium powder：By the ZrO of surface cationic2Powder is slowly added to negative to surface Among the titanium oxide sol of electric charge, the ZrO of surface cationic2The weight ratio of powder and colloidal sol is 1：8~12, addition is finished Continue to stir afterwards, then powder is filtered out, decompression drying, obtaining to surface has titania oxide supported Zirconium powder；
6th step, the compacting of base substrate：By weight, by 92~96 parts of surfaces have titania oxide supported Zirconium powder, 1~3 part SnO2Powder, 2~3 parts of polyvinyl alcohol, 3~5 parts of ethanol are well mixed, and as powder mixture, and carry out dry-pressing in a mold Shaping, the demoulding, obtains base substrate；
7th step, sintering：Base substrate is calcined in air atmosphere, full ceramic restoration material is obtained.
In the 1st described step, ZrO after high-energy ball milling2、SnO2The average grain diameter of powder is not more than 10 μm.
In the 2nd described step, glyoxaline ion liquid be selected from chlorination -1- pi-allyl -3- methylimidazoles or chlorination 1- butyl - One or more of mixing in 3- methylimidazoles；Described alcohols solvent is selected from methanol, ethanol, propane diols, butanol or isoamyl One or more of mixing in alcohol.
In the 3rd described step, ZrO2The weight ratio of the solution for the ionic liquid that powder is grafted with silane coupler is 1：2~ 4；Process step refers to handle 3~6h under the conditions of 75~80 DEG C.
In the 4th described step, the temperature of hydrolysis is 55~60 DEG C, and hydrolysis time is 2~4h；Modified-reaction Temperature is 35~40 DEG C, and the modified-reaction time is 1~3h.
In the 5th described step, whipping process feed temperature is 40~50 DEG C, and mixing time is 5~10h.
In the 6th described step, dry-pressing formed 500~700MPa of pressure, 20~30s of pressing time.
In the 7th described step, sintering procedure is：950~1100 DEG C and insulation 2 are first warming up to 3~5 DEG C/min speed ~4 hours, room temperature is then cooled to 2~4 DEG C/min speed.
Beneficial effect
In the preparation method of the present invention, the effect of the 1st step is that the particle diameter for making powder diminishes, beneficial to the even tissue of sintering process Change；The effect of 2nd step is make ionic liquid silicane coupling agent surface grafted；The effect of 3rd step is by silane coupler Effect is grafted with zirconium surface；The effect of 4th step is to prepare titanium oxide sol, wherein due to the effect of electric double layer, band The surface of the titanium oxide sol particle of negative electricity is modified with one layer of positive charge by the surface of hydroxy silicon oil, and destruction electric double layer is made With, make particle surface negatively charged, regulation pH purpose be to make in the basic conditions, particle be in negative electrical charge；The effect of 5th step is Titanium oxide sol is coated on by the method for electrostatic self-assembled by the surface of Zirconium powder, can be obtained in sintering process The snap action of titanium oxide sol, improves the amalgamation between Zirconium powder and aggregate；The effect of 6th step is by pressed by powder Into wet embryo body；The effect of 7th step is sinter molding.
The present invention proposes a kind of preparation method of the dental all-ceramics repair materials based on electrostatic self-assembled technology, use Key technology is to make one layer of titanium oxide sol particle of Surface coating of zirconia material by the method for electrostatic self-assembled, by burning The overlap joint of titanium oxide sol during knot, the material for solving thermal coefficient of expansion difference between zirconium oxide and other aggregates and bringing Easy to crack the problem of.
Brief description of the drawings
Fig. 1 is the surface SEM figures for the dental prosthetic material that embodiment 3 is prepared；
Fig. 2 is the surface SEM figures for the dental prosthetic material that reference examples 1 are prepared.
Embodiment
Embodiment 1
1st step, the pretreatment of powder：Take ZrO2Powder, SnO2Powder, is dispersed in water respectively, and solid content is configured to respectively and is Slurry is filtered out after 10% slurry, ball milling, after spray drying, the ZrO after ball milling is respectively obtained2、SnO2Powder, high energy ball ZrO after mill2、SnO2About 5~10 μm of the average grain diameter of powder；
2nd step, the preparation of the ionic liquid of silane coupler grafting：In ethanol, add 2wt% Silane coupling agent KH550 and 6% chlorination -1- pi-allyl -3- methylimidazoles, react after 12h at 85 DEG C, obtain the ionic liquid of silane coupler grafting Solution；
3rd step, ZrO2The surface cationic of powder：By the ZrO after ball milling2Powder is immersed in the ion of silane coupler grafting In the solution of liquid, 3h, ZrO are handled under the conditions of 75 DEG C2The weight of the solution for the ionic liquid that powder is grafted with silane coupler It is 1 to measure ratio：2, obtain the ZrO of surface cationic2Powder；
4th step, the preparation of the titanium oxide sol of negative electrical charge：By weight, by 30 parts of butyl titanate, 10 parts of sodium sulphate and 350 parts of water is well mixed, after heating, and sulfuric acid solution is added dropwise to the pH of system 4~5, reaction, the temperature of hydrolysis is hydrolyzed Degree is 55 DEG C, and hydrolysis time is 2h；It is cooled to after room temperature, adds 20 parts of hydroxy silicon oil, be modified reaction, modified-reaction Temperature be 35 DEG C, the modified-reaction time is 1h, by reaction solution be concentrated under reduced pressure into before volume is 40%, add NaOH molten Liquid adjusts pH to 91~1, obtains the titanium oxide sol of surface negative charge；
5th step, the surface electrostatic self assembly of Zirconium powder：By the ZrO of surface cationic2Powder is slowly added to negative to surface Among the titanium oxide sol of electric charge, the ZrO of surface cationic2The weight ratio of powder and colloidal sol is 1：8, addition finishes follow-up Continuous stirring, whipping process feed temperature is 40 DEG C, and mixing time is 5h, then powder is filtered out, and decompression drying obtains surface aerobic Change the Zirconium powder of titanium load；
6th step, the compacting of base substrate：By weight, 92 parts of surfaces there are into titania oxide supported Zirconium powder, 1 part of SnO2Powder Body, 2 parts of polyvinyl alcohol, 3 parts of ethanol are well mixed, as powder mixture, and carry out in a mold it is dry-pressing formed, it is dry-pressing formed Pressure 500MPa, pressing time 20s, the demoulding, obtain base substrate；
7th step, sintering：Base substrate is calcined in air atmosphere, sintering procedure is：First it is warming up to 3 DEG C/min speed 950 DEG C and be incubated 2 hours, room temperature is then cooled to 2 DEG C/min speed, full ceramic restoration material is obtained.
Embodiment 2
1st step, the pretreatment of powder：Take ZrO2Powder, SnO2Powder, is dispersed in water respectively, and solid content is configured to respectively and is Slurry is filtered out after 10~15% slurry, ball milling, after spray drying, the ZrO after ball milling is respectively obtained2、SnO2Powder is high ZrO after energy ball milling2、SnO2About 5~10 μm of the average grain diameter of powder；
2nd step, the preparation of the ionic liquid of silane coupler grafting：In ethanol, add 4wt% Silane coupling agent KH550 and 8% chlorination -1- pi-allyl -3- methylimidazoles, react after 16h at 90 DEG C, obtain the ionic liquid of silane coupler grafting Solution；
3rd step, ZrO2The surface cationic of powder：By the ZrO after ball milling2Powder is immersed in the ion of silane coupler grafting In the solution of liquid, 6h, ZrO are handled under the conditions of 80 DEG C2The weight of the solution for the ionic liquid that powder is grafted with silane coupler It is 1 to measure ratio：4, obtain the ZrO of surface cationic2Powder；
4th step, the preparation of the titanium oxide sol of negative electrical charge：By weight, by 45 parts of butyl titanate, 12 parts of sodium sulphate and 450 parts of water is well mixed, after heating, and sulfuric acid solution is added dropwise to the pH of system 4~5, reaction, the temperature of hydrolysis is hydrolyzed Degree is 60 DEG C, and hydrolysis time is 4h；It is cooled to after room temperature, adds 25 parts of hydroxy silicon oil, be modified reaction, modified-reaction Temperature be 40 DEG C, the modified-reaction time is 3h, by reaction solution be concentrated under reduced pressure into before volume is 50%, add NaOH molten Liquid adjusts pH to 9~11, obtains the titanium oxide sol of surface negative charge；
5th step, the surface electrostatic self assembly of Zirconium powder：By the ZrO of surface cationic2Powder is slowly added to negative to surface Among the titanium oxide sol of electric charge, the ZrO of surface cationic2The weight ratio of powder and colloidal sol is 1：12, after addition is finished Continue to stir, whipping process feed temperature is 50 DEG C, and mixing time is 10h, then powder is filtered out, and decompression drying obtains surface There is titania oxide supported Zirconium powder；
6th step, the compacting of base substrate：By weight, 96 parts of surfaces there are into titania oxide supported Zirconium powder, 3 parts of SnO2Powder Body, 3 parts of polyvinyl alcohol, 5 parts of ethanol are well mixed, as powder mixture, and carry out in a mold it is dry-pressing formed, it is dry-pressing formed Pressure 700MPa, pressing time 30s, the demoulding, obtain base substrate；
7th step, sintering：Base substrate is calcined in air atmosphere, sintering procedure is：First it is warming up to 5 DEG C/min speed 1100 DEG C and be incubated 4 hours, room temperature is then cooled to 4 DEG C/min speed, full ceramic restoration material is obtained.
Embodiment 3
1st step, the pretreatment of powder：Take ZrO2Powder, SnO2Powder, is dispersed in water respectively, and solid content is configured to respectively and is Slurry is filtered out after 10~15% slurry, ball milling, after spray drying, the ZrO after ball milling is respectively obtained2、SnO2Powder is high ZrO after energy ball milling2、SnO2About 5~10 μm of the average grain diameter of powder；
2nd step, the preparation of the ionic liquid of silane coupler grafting：In ethanol, add 3wt% Silane coupling agent KH550 and 7% chlorination -1- pi-allyl -3- methylimidazoles, react after 15h at 88 DEG C, obtain the ionic liquid of silane coupler grafting Solution；
3rd step, ZrO2The surface cationic of powder：By the ZrO after ball milling2Powder is immersed in the ion of silane coupler grafting In the solution of liquid, 5h, ZrO are handled under the conditions of 78 DEG C2The weight of the solution for the ionic liquid that powder is grafted with silane coupler It is 1 to measure ratio：3, obtain the ZrO of surface cationic2Powder；
4th step, the preparation of the titanium oxide sol of negative electrical charge：By weight, by 35 parts of butyl titanate, 11 parts of sodium sulphate and 380 parts of water is well mixed, after heating, and sulfuric acid solution is added dropwise to the pH of system 4~5, reaction, the temperature of hydrolysis is hydrolyzed Degree is 58 DEG C, and hydrolysis time is 3h；It is cooled to after room temperature, adds 22 parts of hydroxy silicon oil, be modified reaction, modified-reaction Temperature be 38 DEG C, the modified-reaction time is 2h, by reaction solution be concentrated under reduced pressure into before volume is 45%, add NaOH molten Liquid adjusts pH to 9~11, obtains the titanium oxide sol of surface negative charge；
5th step, the surface electrostatic self assembly of Zirconium powder：By the ZrO of surface cationic2Powder is slowly added to negative to surface Among the titanium oxide sol of electric charge, the ZrO of surface cationic2The weight ratio of powder and colloidal sol is 1：10, after addition is finished Continue to stir, whipping process feed temperature is 45 DEG C, and mixing time is 8h, then powder is filtered out, decompression drying, and obtaining to surface has Titania oxide supported Zirconium powder；
6th step, the compacting of base substrate：By weight, by 92~96 parts of surfaces have titania oxide supported Zirconium powder, 2 parts SnO2Powder, 3 parts of polyvinyl alcohol, 4 parts of ethanol are well mixed, as powder mixture, and carry out in a mold dry-pressing formed, are done Molded pressure 600MPa, pressing time 25s, the demoulding, obtain base substrate；
7th step, sintering：Base substrate is calcined in air atmosphere, sintering procedure is：First it is warming up to 4 DEG C/min speed 980 DEG C and be incubated 3 hours, room temperature is then cooled to 3 DEG C/min speed, full ceramic restoration material is obtained.
Reference examples 1
Difference with embodiment 3 is：Not by way of electrostatic self-assembled in Zirconium powder area load titanium oxide, but In the process for being added to idiosome compacting directly as aggregate using a certain amount of titanium oxide powder.
1st step, the pretreatment of powder：Take ZrO2Powder, SnO2Powder, is dispersed in water respectively, and solid content is configured to respectively For 10~15% slurry, slurry is filtered out after ball milling, after spray drying, the ZrO after ball milling is respectively obtained2、SnO2Powder, ZrO after high-energy ball milling2、SnO2About 5~10 μm of the average grain diameter of powder；
2nd step, the preparation of the ionic liquid of silane coupler grafting：In ethanol, add 3wt% Silane coupling agent KH550 and 7% chlorination -1- pi-allyl -3- methylimidazoles, react after 15h at 88 DEG C, obtain the ionic liquid of silane coupler grafting Solution；
3rd step, ZrO2The surface cationic of powder：By the ZrO after ball milling2Powder is immersed in the ion of silane coupler grafting In the solution of liquid, 5h, ZrO are handled under the conditions of 78 DEG C2The weight of the solution for the ionic liquid that powder is grafted with silane coupler It is 1 to measure ratio：3, obtain the ZrO of surface cationic2Powder；
4th step, the preparation of the titanium oxide sol of negative electrical charge：By weight, by 35 parts of butyl titanate, 11 parts of sodium sulphate and 380 parts of water is well mixed, after heating, and sulfuric acid solution is added dropwise to the pH of system 4~5, reaction, the temperature of hydrolysis is hydrolyzed Degree is 58 DEG C, and hydrolysis time is 3h；It is cooled to after room temperature, adds 22 parts of hydroxy silicon oil, be modified reaction, modified-reaction Temperature be 38 DEG C, the modified-reaction time is 2h, by reaction solution be concentrated under reduced pressure into before volume is 45%, add NaOH molten Liquid adjusts pH to 9~11, obtains the titanium oxide sol of surface negative charge；
5th step, the preparation of titanium oxide powder：Take after the titanium oxide sol of 10 times of ZrO2 powders weight, decompression drying, aoxidized Titanium valve body；
6th step, the compacting of base substrate：By weight, 92~96 parts of surfaces there are into titania oxide supported Zirconium powder, the 5th step Obtained titanium oxide powder, 2 parts of SnO2Powder, 3 parts of polyvinyl alcohol, 4 parts of ethanol are well mixed, as powder mixture, and Dry-pressing formed, dry-pressing formed pressure 600MPa, pressing time 25s are carried out in mould, is stripped, obtains base substrate；
7th step, sintering：Base substrate is calcined in air atmosphere, sintering procedure is：First it is warming up to 4 DEG C/min speed 980 DEG C and be incubated 3 hours, room temperature is then cooled to 3 DEG C/min speed, full ceramic restoration material is obtained.
Reference examples 2
Difference with embodiment 3 is：Titanium oxide sol is not carried out hydroxyl silicon oil modified.
1st step, the pretreatment of powder：Take ZrO2Powder, SnO2Powder, is dispersed in water respectively, and solid content is configured to respectively For 10~15% slurry, slurry is filtered out after ball milling, after spray drying, the ZrO after ball milling is respectively obtained2、SnO2Powder, ZrO after high-energy ball milling2、SnO2About 5~10 μm of the average grain diameter of powder；
2nd step, the preparation of the ionic liquid of silane coupler grafting：In ethanol, add 3wt% Silane coupling agent KH550 and 7% chlorination -1- pi-allyl -3- methylimidazoles, react after 15h at 88 DEG C, obtain the ionic liquid of silane coupler grafting Solution；
3rd step, ZrO2The surface cationic of powder：By the ZrO after ball milling2Powder is immersed in the ion of silane coupler grafting In the solution of liquid, 5h, ZrO are handled under the conditions of 78 DEG C2The weight of the solution for the ionic liquid that powder is grafted with silane coupler It is 1 to measure ratio：3, obtain the ZrO of surface cationic2Powder；
4th step, the preparation of the titanium oxide sol of negative electrical charge：By weight, by 35 parts of butyl titanate, 11 parts of sodium sulphate and 380 parts of water is well mixed, after heating, and sulfuric acid solution is added dropwise to the pH of system 4~5, reaction, the temperature of hydrolysis is hydrolyzed Degree is 58 DEG C, and hydrolysis time is 3h；It is cooled to after room temperature, then is warming up to 38 DEG C, keeps 2h, reaction solution is concentrated under reduced pressure into Volume be before 45%, add NaOH solution regulation pH to 9~11, obtain the titanium oxide sol of surface negative charge；
5th step, the surface electrostatic self assembly of Zirconium powder：By the ZrO of surface cationic2Powder is slowly added to negative to surface Among the titanium oxide sol of electric charge, the ZrO of surface cationic2The weight ratio of powder and colloidal sol is 1：10, after addition is finished Continue to stir, whipping process feed temperature is 45 DEG C, and mixing time is 8h, then powder is filtered out, decompression drying, and obtaining to surface has Titania oxide supported Zirconium powder；
6th step, the compacting of base substrate：By weight, by 92~96 parts of surfaces have titania oxide supported Zirconium powder, 2 parts SnO2Powder, 3 parts of polyvinyl alcohol, 4 parts of ethanol are well mixed, as powder mixture, and carry out in a mold dry-pressing formed, are done Molded pressure 600MPa, pressing time 25s, the demoulding, obtain base substrate；
7th step, sintering：Base substrate is calcined in air atmosphere, sintering procedure is：First it is warming up to 4 DEG C/min speed 980 DEG C and be incubated 3 hours, room temperature is then cooled to 3 DEG C/min speed, full ceramic restoration material is obtained.
As can be seen from the table, the full ceramic restoration material that the present invention is provided has preferable intensity and toughness；Embodiment 3 relative to For reference examples 1, due to by the titania oxide supported surface in zirconium oxide, can improve its in sintering process with other aggregates it Between conformability, by the snap action of titanium oxide can preferably make material intensity and toughness improve；Embodiment 3 relative to For reference examples 2, titanium oxide sol is modified by hydroxy silicon oil, the electric double layer effect of sol surface can be offset, made The negative charge amount of sol particle is improved, and is made preferably to coat Zirconium powder during electrostatic self-assembled, is improved material The intensity and toughness of material.
The surface electromicroscopic photograph for the full ceramic restoration material that embodiment 3 is prepared is as shown in Figure 1, it can be seen that surface is The graininess mutually overlapped, smooth zero defect；The material surface that reference examples 1 are prepared there are obvious crackle, illustrate oxygen Change titanium has the effect for preferably preventing material sintering cracking for the electrostatic self-assembled of zirconium oxide.

Claims (8)

1. a kind of preparation method of the dental all-ceramics repair materials based on electrostatic self-assembled technology, it is characterised in that including as follows Step：
1st step, the pretreatment of powder：Take ZrO2Powder, SnO2Powder, is dispersed in water respectively, and it is 10 that solid content is configured to respectively Slurry is filtered out after~15% slurry, ball milling, after spray drying, the ZrO after ball milling is respectively obtained2、SnO2Powder；
2nd step, the preparation of the ionic liquid of silane coupler grafting：In alcohols solvent, 2~4wt% silane coupler is added Glyoxaline ion liquid with 6~8%, reacts after 12~16h at 85~90 DEG C, obtains the ionic liquid of silane coupler grafting The solution of body；
3rd step, ZrO2The surface cationic of powder：By the ZrO after ball milling2Powder is immersed in the ion of silane coupler grafting Handled in the solution of liquid, obtain the ZrO of surface cationic2Powder；
4th step, the preparation of the titanium oxide sol of negative electrical charge：By weight, by 30~45 parts of butyl titanate, sodium sulphate 10 ~12 parts well mixed with 350~450 parts of water, after heating, and sulfuric acid solution is added dropwise to the pH of system 4~5, is hydrolyzed anti- Should；It is cooled to after room temperature, adds 20~25 parts of hydroxy silicon oil, be modified reaction, reaction solution is concentrated under reduced pressure into volume for it Preceding 40~50%, add NaOH solution regulation pH to 9~11, obtain the titanium oxide sol of surface negative charge；
5th step, the surface electrostatic self assembly of Zirconium powder：By the ZrO of surface cationic2Powder is slowly added to negative to surface Among the titanium oxide sol of electric charge, the ZrO of surface cationic2The weight ratio of powder and colloidal sol is 1：8~12, addition is finished Continue to stir afterwards, then powder is filtered out, decompression drying, obtaining to surface has titania oxide supported Zirconium powder；
6th step, the compacting of base substrate：By weight, by 92~96 parts of surfaces have titania oxide supported Zirconium powder, 1~3 part SnO2Powder, 2~3 parts of polyvinyl alcohol, 3~5 parts of ethanol are well mixed, and as powder mixture, and carry out dry-pressing in a mold Shaping, the demoulding, obtains base substrate；
7th step, sintering：Base substrate is calcined in air atmosphere, full ceramic restoration material is obtained.
2. the preparation method of the dental all-ceramics repair materials according to claim 1 based on electrostatic self-assembled technology, it is special Levy and be, in the 1st described step, ZrO after high-energy ball milling2、SnO2The average grain diameter of powder is not more than 10 μm.
3. the preparation method of the dental all-ceramics repair materials according to claim 1 based on electrostatic self-assembled technology, it is special Levy and be, in the 2nd described step, glyoxaline ion liquid be selected from chlorination -1- pi-allyl -3- methylimidazoles or chlorination 1- butyl - One or more of mixing in 3- methylimidazoles；Described alcohols solvent is selected from methanol, ethanol, propane diols, butanol or isoamyl One or more of mixing in alcohol.
4. the preparation method of the dental all-ceramics repair materials according to claim 1 based on electrostatic self-assembled technology, it is special Levy and be, in the 3rd described step, ZrO2The weight ratio of the solution for the ionic liquid that powder is grafted with silane coupler is 1：2~ 4；Process step refers to handle 3~6h under the conditions of 75~80 DEG C.
5. the preparation method of the dental all-ceramics repair materials according to claim 1 based on electrostatic self-assembled technology, it is special Levy and be, in the 4th described step, the temperature of hydrolysis is 55~60 DEG C, and hydrolysis time is 2~4h；Modified-reaction Temperature is 35~40 DEG C, and the modified-reaction time is 1~3h.
6. the preparation method of the dental all-ceramics repair materials according to claim 1 based on electrostatic self-assembled technology, it is special Levy and be, in the 5th described step, whipping process feed temperature is 40~50 DEG C, and mixing time is 5~10h.
7. the preparation method of the dental all-ceramics repair materials according to claim 1 based on electrostatic self-assembled technology, it is special Levy and be, in the 6th described step, dry-pressing formed 500~700MPa of pressure, 20~30s of pressing time.
8. the preparation method of the dental all-ceramics repair materials according to claim 1 based on electrostatic self-assembled technology, it is special Levy and be, in the 7th described step, sintering procedure is：950~1100 DEG C and insulation 2 are first warming up to 3~5 DEG C/min speed ~4 hours, room temperature is then cooled to 2~4 DEG C/min speed.
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