Zirconium oxide ceramic material suitable for photocuring additive manufacturing and method for preparing restoration

Abstract

The invention discloses a zirconia ceramic material suitable for photocuring additive manufacturing and a method for preparing a restoration, the zirconia ceramic material comprises the following raw materials: nanometer zirconia powder and photosensitive resin mixed liquor, the content of the nanometer zirconia powder is more than 79wt%; the particle size of the nano zirconium oxide powder is 10 to 400 nanometers. After sintering, an ultrathin restoration with the thickness of 0.1 mm and at least three units of bridge bodies can be prepared without cracking, the interlayer mechanical difference of a sintered ceramic piece is small, the overall precision of the restoration is high, and the application requirement that the overall error of a single restoration is smaller than or equal to 120 microns is met.

Description

Technical Field

[0001] The present invention relates to the technical field of dental material processing, and in particular to a zirconia ceramic material suitable for photocuring additive manufacturing and a method for preparing a restoration. Background Art

[0002] 3D printing, also known as additive manufacturing, is a cutting-edge manufacturing technology that integrates digital modeling technology, information technology, materials science, chemistry and many other fields. The Economist magazine calls it the "third industrial revolution". In recent years, with the development of aerospace, biomedicine and other fields, traditional processing methods can no longer fully meet human requirements. The demand for personalized and customized products has further pushed 3D printing technology to the national strategic level.

[0003] Ceramic materials are widely used in aerospace, electronics, biomedicine and other fields due to their high hardness, high strength, extremely high corrosion resistance and wear resistance. However, it is difficult to form complex precision ceramic parts with traditional processes. 3D printing, as a new molding technology, has great advantages in preparing high-precision parts of arbitrary shapes and can meet personalized needs. Among the different ceramic 3D printing technologies, there are few methods that can manufacture fully dense ceramics, among which stereolithography is one of the most promising technologies. Stereolithography is a relatively mature additive manufacturing technology, mainly used to manufacture polymer parts. These technologies can be divided into stereolithography (SLA) based on point scanning and digital light processing (DLP) based on mask image projection. Both use the photocuring reaction of photosensitive resins to complete the manufacturing through layer-by-layer "printing" and accumulation. The latter usually has a faster molding speed and is suitable for the manufacture of small components, especially for the manufacture of dental restorations.

[0004] CN106007671B discloses a ceramic composite material for 3D printing and a preparation method thereof, which includes the following components by weight: 20 to 45 parts of acrylate monomer; 121 to 165 parts of ceramic powder; 10 to 20 parts of spirocarbonate expansion monomer; 2 to 14 parts of dispersant; 1 to 3 parts of photoinitiator; 0 to 3 parts of photoinhibitor; and 1 to 3 parts of ultraviolet light absorber. The above-mentioned ceramic composite material for 3D printing has a small curing shrinkage and a short curing time, so it is suitable for investment casting. Under the irradiation of ultraviolet light, the free radical photoinitiator of the above-mentioned ceramic composite material for 3D printing initiates the polymerization of the acrylate monomer and thus cures rapidly. At the same time, the expansion monomer can produce volume expansion during the polymerization process initiated by the cationic photoinitiator, thereby reducing the shrinkage and internal stress generated by the slurry during curing, so that the printed parts have smaller deformation, better dimensional accuracy and fewer microcrack defects. This method only solves the problem of polymerization shrinkage by expanding monomers, but does not solve the problem of practical application of 3D printed ceramic restorations. Usually, the use of expanding monomers will reduce the density of the green body, and the green body strength is not enough to make thin-walled parts. In addition, the final density of the finished product is not high, which affects the mechanical properties.

[0005] CN106810215B discloses a method for preparing a ceramic slurry and 3D printing photocuring. It mainly includes: ceramic powder: 25-85vol%, photosensitive resin premix: 15-75vol%. It includes the following steps: A) Preparation of photosensitive resin premix: oligomer, active diluent, photoinitiator, dispersant, photosensitizer and sensitizer are stirred at medium speed for 0.5-3h in a certain ratio to make each component fully mixed; B) the above premix and ceramic powder are placed in a ball mill in a certain volume ratio, and ball milled for 5-15h to prepare a ceramic slurry with high solid content and low viscosity. Then, it is cured layer by layer on a 3D photocuring molding machine to obtain a ceramic green body, and finally a ceramic part is obtained by post-treatment such as drying, degreasing and sintering. This method only solves the problem of 3D printing ceramic debinding, and does not solve the problems of practical application of 3D printing ceramic restorations such as accuracy and cracking of large-size samples. Moreover, the post-infiltration method to increase density is complex and not practical for the production of oral restorations.

[0006] CN106966709B discloses a method for preparing transparent alumina ceramics based on 3D printing of photocuring, comprising the following steps: a) subjecting photosensitive alumina ceramic slurry to photocuring forming by a photocuring forming machine to obtain a formed body; the exposure time of the photocuring forming is 2 to 15 seconds, and the layer thickness is 10 to 100 μm; b) subjecting the formed body to thermal degreasing to obtain a degreasing body; c) subjecting the degreasing body to cold isostatic pressing to obtain an intermediate body; d) subjecting the intermediate body to a heat treatment process; The impregnation solution is infiltrated to obtain an impregnation body; the impregnation solution is a mixed solution of magnesium salt, yttrium salt and lanthanum salt; e) the impregnation body is heated to 1300-1650°C at a heating rate of 10-15°C / min and is kept warm once, and then cooled to 800-1000°C at a cooling rate of 10-15°C / min to obtain a primary sintered body; the primary sintered body is heated to 1150-1550°C at a heating rate of 10-15°C / min and is kept warm twice to obtain a transparent alumina ceramic. This method is complicated to operate and is not suitable for mass production applications for oral restorations.

[0007] CN109485433B discloses a ceramic slurry for photocuring 3D printing and a preparation method thereof, the method comprising: taking acrylamide and N,N'-methylenebisacrylamide and dissolving them in deionized water in a mass ratio of the total mass of the two to water, and adding a leveling agent and a defoaming agent in a certain proportion of the mass of the previous solution. Weigh submicron ceramic powder, weigh a dispersant in a certain proportion of the total mass of the ceramic powder and dissolve it in the solution of the previous step, add the ceramic powder in steps and ball mill, then add a certain proportion of the total mass of the ceramic powder and continue ball milling after adjusting the pH to form a ceramic slurry with a specified solid content, add a photoinitiator and ball mill to obtain a photocuring slurry with a high solid content and low viscosity. This method only solves the solid content and viscosity problems of 3D printing ceramic slurry, and does not solve the problems of practical application of 3D printing ceramic restorations such as accuracy, cracking of large-size samples, etc.

[0008] It can be found from the above-mentioned prior art that in the patents related to 3D printing materials, most inventions and research focus on the improvement of photocurable printing slurry (such as solid content) or material properties (mechanical properties) after sintering. However, there are few patents on the application of specific oral restorations. In addition, compared with traditional milling and casting technology, the biggest advantage of DLP printing is that it can form fine parts, which is very suitable for the application of ultra-thin oral restorations.

[0009] However, the successful application of actual ceramic light-curing additive manufacturing parts must solve the problems in the entire process from printing slurry - printing green body - printing debinding sintering - oral restoration performance, not just a certain point or a certain process section. Specifically, the application of light-curing 3D printing technology to the preparation of ceramic restorations has the following unresolved problems in existing technical solutions: For slurry: the solid content of the material must be high and the viscosity must be low, which is the basic requirement for preparing ceramic printed parts. However, the influence of powder, resin and additive formula on the later green body performance, printing accuracy, debinding and sintering performance must also be considered.

[0010] For printing green bodies: the green bodies need to have sufficient strength and toughness to meet the needs of preparing small-sized products such as oral restorations. Especially for ultra-thin restorations (<0.3mm), the strength and toughness of the green bodies are required to be higher.

[0011] Since the principle of photocuring is to form a predetermined projection pattern by projecting light onto the surface of the colloidal slurry, controlling the scattering and transmission of the projection light in the colloidal slurry plays a key role in controlling the final accuracy.

[0012] Regarding cracking caused by glue removal: Since the light-cured 3D ceramic slurry usually contains more than 21% organic matter, these organic matter need to be removed in the later heat treatment stage. When removing, it is very easy to cause cracking. For large-sized oral restorations, such as 3-unit bridges, the cracking problem must be solved.

[0013] Regarding the performance of the finished product after sintering: ① The relative density of the sintered product must be high enough, usually reaching a relative density of more than 99%, to meet the requirements of mechanical and biological properties. ② In addition, due to the layer-by-layer stacking characteristics of 3D printing, when the force direction is perpendicular to the stacking direction, the interlayer bonding failure is very likely to occur for the bending strength of ceramics. This will eventually lead to obvious directional performance differences in bending strength, and the minimum bending strength requirements of the restoration will not be met in the 90° printing direction. Summary of the invention

[0014] The purpose of the present invention is to provide a zirconia ceramic material suitable for photocuring additive manufacturing and a method for preparing a restoration. After sintering, an ultra-thin restoration with a thickness of 0.1 mm and at least 3 units of bridge bodies without cracking can be prepared. After sintering, the mechanical difference between the layers of the ceramic parts is small, the overall accuracy of the restoration is high, and the application requirement of the overall error of a single restoration is ≤120um is met.

[0015] The technical solution adopted by the present invention to solve the technical problem is: A zirconia ceramic material suitable for photocuring additive manufacturing, wherein the raw material is composed of a mixture of nano-zirconia powder and a photosensitive resin, wherein the content of the nano-zirconia powder is more than 79wt%; The particle size of the nano zirconium oxide powder is 10-400 nanometers; In parts by weight, the photosensitive resin mixture is prepared by mixing 0.6 to 3 parts of a monofunctional monomer, 2.4 to 12 parts of a multifunctional monomer, 1 to 6 parts of a prepolymer, 0.5 to 12 parts of a dispersant, 0.5 to 12 parts of a plasticizer, 0.05 to 0.5 parts of a photoinitiator, 0.01 to 0.5 parts of a light absorber, 0.001 to 0.1 parts of a light inhibitor, and 0.001 to 0.1 parts of upconversion particles.

[0016] The nano zirconium oxide powder is used after being pretreated, and the pretreatment method is as follows: (1) Dry the nano zirconium oxide powder to a moisture content of ≤1%; (2) 100 parts of anhydrous ethanol and 0.1-6 parts of a surface modifier are mixed by weight, and then 30-80 parts of dried nano zirconium oxide powder are added, stirred at 50-80° C. for 2-6 hours, centrifuged, the supernatant is discarded, and dried; (3) adding the dried nano zirconium oxide powder to 100 parts by weight of anhydrous ethanol, ultrasonically dispersing, centrifuging, discarding the supernatant, and drying; repeating this step 2-3 times; (4) Dry the nano zirconium oxide powder processed in step (3) for more than 6 hours, grind it mechanically, sieve it and set it aside.

[0017] The surface modifier is selected from one or more of stearic acid, oleic acid, titanate coupling agent, silane coupling agent, aluminate coupling agent, zirconate coupling agent, aluminum-titanium composite coupling agent, sulfonated castor oil, and monolipid phosphate.

[0018] The monofunctional monomer is selected from one or more of 2-hydroxyethyl acrylate (HEA), 2-hydroxypropyl acrylate (HPA), lauryl acrylate (LA), glycidyl acrylate (GA), isobornyl acrylate (IBOA), tetrahydrofurfuryl acrylate (THFA), dioxazolidinone acrylate, isobornyl acrylate (IBOA), and cyclotrimethylolpropane formal acrylate (CTFA).

[0019] The multifunctional monomer is selected from one or more of 1,6-hexanediol diacrylate (HDDA), hydroxyethyl methacrylate (HEMA), ethoxylated pentaerythritol tetraacrylate (PPTTA), dipentaerythritol hexaacrylate (DPHA), trimethylolpropane triacrylate (TMPTA), ethoxylated trimethylolpropane triacrylate (TMP6EOTA), and polyethylene glycol diacrylate (PEGDA).

[0020] The prepolymer is selected from one or more of polyurethane acrylate, polyester acrylate and epoxy acrylate.

[0021] The dispersant is selected from one or more of polyether dispersants (Solsperse series of Lubrizol, polyester dispersants (Hypersol of KVK of Denmark, DISPER BKY series of BYK of Germany), polyacrylate dispersants (Disperse-AVD series of Daniel of the United States and Elvacite series of DuPont, DISPERBKY of BYK of Germany), and polyolefin dispersants (HYPODTM series of Dow Chemical Company); The plasticizer is selected from one or more of polyaliphatic hydrocarbons, polyethylene glycol, polypropylene glycol, tributyl citrate, diisononyl cyclohexane 1,2-dicarboxylate, and epoxidized soybean oil.

[0022] The photoinitiator is selected from any one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMBA), 1-hydroxy-cyclohexyl benzophenone (UV-184), 2-hydroxy-2-methyl-p-hydroxyethyl ether phenyl acetone-1, and 2,4,6-(trimethylbenzoyl) diphenyl phosphine oxide (TPO); The light absorber is selected from ethylhexyl salicylate, trimethylcyclohexyl salicylate, octyl salicylate, phenyl salicylate, isohexadecanyl salicylate, hexyl salicylate, ethylene glycol salicylate, benzyl salicylate, benzophenone-3 (UV-327), benzophenone-4 (UV-9), benzophenone-8 (UV-5411), benzophenone-5 (BP-5), 2,2'-methylenebis(4-tert-octyl-6-benzotriazolephenol (UV360), 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole (UV329), 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol (UV-928), 2-(2'-hydroxy- 3',5'-bis(a,a-dimethylbenzyl)phenyl)benzotriazole (UV-234), 2-(2'-hydroxy-5'-tert-octylphenyl)-5-chlorophenyl-2H-triazine (UV1557), 2,4-diphenyl-6-(2-hydroxyphenyl)-1,3,5-triazine (UV1164), 2,2'-hydroxy-5,5'-diphenyl-1,3,5-triazine (UV360), 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (UV400), 2,4-bis-(2-ethylhexyloxy)-6-(2-hydroxyphenyl)-1,3,5-triazine (UV479), Tinuvin123, Tinuvin 144. One or more of bis(2,2,6,6-tetramethylpiperidinyl) sebacate (UV770) and Chimassorb 119; The photoinhibitor is selected from one or more of tetraethylthiuram disulfide, naphthoyl methylene quinuclidine tetraphenyl borate, p-methoxyphenol, 2,4,6-trinitrophenol, 1,4-benzoquinone, hydroquinone, and 2,6-di-tert-butyl-p-cresol; the up-conversion particle is selected from one or more of zirconium oxide doped with trivalent rare earth ions, yttrium oxide doped with trivalent rare earth ions, lanthanum oxychloride doped with trivalent rare earth ions, and yttrium oxysulfide doped with trivalent rare earth ions, and the trivalent rare earth ion is Yb 3 +, Er 3 +, Ho3+ and Tm 3 + one of the above (the upconversion particles are commercially available materials, purchased from Xi'an Qiyue Biotechnology, Hangzhou Xinqiao Biotechnology Co., Ltd., etc.).

[0023] The method for manufacturing a ceramic oral restoration from a zirconium oxide ceramic material comprises the following steps: 1. Preparation of light-curing ceramic slurry: Mix the nano zirconium oxide powder and the photosensitive resin mixture evenly, sieve, and vacuum degas to obtain the light-curing ceramic slurry; 2. Preparation of the molding body: Using the light-cured ceramic slurry as the raw material, light-cured molding is performed layer by layer on a 3D light-curing molding machine according to the designed restoration shape to obtain the molding body, which is then cleaned with ultrasonic cleaning; 3. Debinding: The molded body is debinded by heat preservation in sections in air, argon, nitrogen or vacuum environment; 4. Sintering: Three-stage sintering The first sintering stage: heating to 200-400℃ at a rate of 1-100℃ / min and keeping at this temperature for 0.5-10h; the purpose is to make the organic content in the sample ≤0.1wt%; The second sintering stage: the temperature is raised to 1100-1400℃ at a rate of 5-200℃ / min, and kept at this temperature for 0.5-10h. The surface can be fully sintered before sealing. The pore distribution inside and outside the sintered body tends to be consistent, and there is no obvious difference in the porosity and pore size inside and outside. In particular, it is necessary to fully eliminate the larger pores between the printed layers at this stage. At this time, the relative density of the green body is about 70-95%; The third sintering stage: heating to 1400-1700℃ at a rate of 5-200℃ / min, keeping warm for 0.5-10h 5. Grinding and polishing: Grind and polish the sintered restoration.

[0024] The section insulation parameters are controlled as follows: First debonding point: heat up to 100-150℃ at a rate of 0.05-10℃ / min, and keep warm for 0.5-10h; Second glue discharge section point: heat up to 180-280℃ at a rate of 0.05-10℃ / min, and keep warm for 0.5-10h; The third glue discharge section point: heat up to 300-380℃ at a rate of 0.05-10℃ / min, and keep warm for 0.5-10h; Fourth row of glue segmentation point: heat up to 400-600℃ at a rate of 0.05-10℃ / min and keep warm for 0.5-10h.

[0025] The present invention is improved as follows: 1. Prepare high solid content (zirconia content ≧79%wt) and low viscosity (<20Pa*S) printing slurry through high solid content, dispersion in non-polar solvent system, and low viscosity photosensitive resin; 2. Nanopowder particles (<405nm) can increase the green body strength. At the same time, linear monomers (monofunctional monomers) and multifunctional monomers and prepolymers with spatial network structures in photosensitive resins can enhance the cross-linking degree of the resin skeleton after curing. The two work synergistically to improve the green body strength at the same time. 3. The combination of single-functional monomers (slow curing speed), multi-functional monomers (medium curing speed) and prepolymers (fast curing speed) in the photosensitive resin can achieve higher green body and sintering density through the difference in curing speed and molecular size after curing; 4. The particle size of nano powder is smaller than the projection wavelength (<405nm wavelength of light-curing projection) to reduce the scattering of powder particles on the projection. It is further combined with light absorbers, upconversion particles and light inhibitors to reduce the miscuring caused by scattering and improve the actual printing accuracy. 5. Use prepolymer to reduce shrinkage (shrinkage < 10%) to prevent polymerization stress caused by larger shrinkage. Add plasticizer to weaken the secondary bonds between resin molecules and increase the mobility of resin molecular bonds. The combination of the two can reduce polymerization shrinkage and residual stress, and reduce deformation of later products. 6. The combination of multifunctional monomers and prepolymers has different thermal decomposition temperatures, forming a temperature gradient decomposition mechanism for organic matter (there are at least two thermal decomposition weight loss peaks during green body debinding). There are enough pores at each temperature stage to discharge the gas formed by the thermal decomposition of organic matter, so that at least 3 units of bridge products will not crack after debinding; 7. Multifunctional monomers are used to ensure sufficient curing depth and interlayer bonding during printing. At the same time, during sintering, the sintering process is controlled to avoid the formation of a shell-core structure with the outer surface closing the inner surface pores, ensuring the discharge of interlayer pores, improving the mechanical properties differences caused by the printing direction, and improving the density of the green body; 8. Through the improvement of debinding process, the printed parts can be printed without cracking in air atmosphere, the process is simple to operate, saving time and energy.

[0026] The beneficial effects of the present invention are: 1. Able to prepare oral restorations with a thickness of up to 0.1 mm; 2. The density of ceramics after sintering can reach 6.0g / cm 3 above; 3. After sintering, at least 3 units of bridge can be prepared without cracking; 3. After sintering, the mechanical difference between the layers of ceramic parts is small. The bending strength of 0° printing can reach more than 800MPa. In the worst case, the bending strength can reach more than 700Mpa when printing at 90°, which meets the actual application requirements of oral restorations. 4. The overall precision of the restoration is high, meeting the application requirement that the overall error of a single restoration is ≤120um. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 is a schematic diagram of a three-unit bridge processed in Example 55; Figure 2is a schematic diagram of a three-unit bridge processed in Example 2; Figure 3 is a schematic diagram of an ultra-thin restoration processed in Example 56; Figure 4 is a schematic diagram of an ultra-thin restoration processed in comparative example 3; Figure 5 is a cross-sectional microstructure diagram of Example 59 after sintering; Figure 6 This is a cross-sectional microstructure diagram of comparative example 4 after sintering; Figure 7 This is the cross-sectional microstructure diagram of Example 5 after sintering. DETAILED DESCRIPTION

[0028] The technical solution of the present invention is further described in detail below through specific embodiments.

[0029] In the present invention, unless otherwise specified, the raw materials and equipment used can be purchased from the market or are commonly used in the art. The methods in the following embodiments, unless otherwise specified, are all conventional methods in the art. In the following embodiments, the upconversion particles are all commercially available materials, trade name: rare earth doped upconversion fluorescent nanoparticles UCNPS, purchased from Xi'an Qiyue Biotechnology, Hangzhou Xinqiao Biotechnology Co., Ltd., etc. For example, trivalent rare earth ions (Yb 3 +) is zirconium oxide: Yb 3 +Upconversion fluorescent nanoparticles.

[0030] Example 1: Pretreatment of Nano-zirconia Powder (1) Drying nano zirconium oxide powder (particle size of about 100 nanometers) to a moisture content of ≤0.1%; (2) 100 kg of anhydrous ethanol and 0.2 kg of a surface modifier (stearic acid) were stirred and mixed at room temperature, and then 50 kg of dried nano zirconium oxide powder was added, stirred at 50° C. for 6 h, centrifuged at 5000 rpm for 15 min, the supernatant was discarded, and the mixture was dried to a moisture content of ≤0.1%; (3) Add all the dried nano-zirconia powder to 100 kg of anhydrous ethanol, disperse by ultrasonication, centrifuge at 5000 rpm for 15 min, discard the supernatant, and dry; repeat this step twice to remove the surface modifier that has not been absorbed; (4) Dry the nano zirconium oxide powder treated in step (3) for more than 6 hours, grind it mechanically, and pass it through an 80-mesh sieve for standby use.

[0031] Example 2: Pretreatment of Nano-zirconia Powder (1) Drying nano zirconium oxide powder (particle size of about 50 nanometers) to a moisture content of ≤0.1%; (2) 100 kg of anhydrous ethanol and 0.1 kg of a surface modifier (oleic acid) were stirred and mixed at room temperature, and then 30 kg of dried nano zirconium oxide powder was added, stirred at 80° C. for 2 h, centrifuged at 5000 rpm for 15 min, the supernatant was discarded, and the mixture was dried to a moisture content of ≤0.1%; (3) Add all the dried nano-zirconia powder to 100 kg of anhydrous ethanol, disperse by ultrasonication, centrifuge at 5000 rpm for 15 min, discard the supernatant, and dry; repeat this step twice to remove the surface modifier that has not been absorbed; (4) Dry the nano zirconium oxide powder treated in step (3) for more than 6 hours, grind it mechanically, and pass it through an 80-mesh sieve for standby use.

[0032] Example 3: Pretreatment of Nano-zirconia Powder (1) Drying nano zirconium oxide powder (particle size of about 400 nanometers) to a moisture content of ≤0.1%; (2) 100 kg of anhydrous ethanol and 6 kg of a surface modifier (titanium ester coupling agent) were stirred and mixed at room temperature, and then 80 kg of dried nano zirconium oxide powder was added, stirred at 60° C. for 4 h, centrifuged at 5000 rpm for 15 min, the supernatant was discarded, and the mixture was dried to a moisture content of ≤0.1%; (3) Add all the dried nano-zirconia powder to 100 kg of anhydrous ethanol, disperse by ultrasonication, centrifuge at 5000 rpm for 15 min, discard the supernatant, and dry; repeat this step 3 times to remove the surface modifier that has not been absorbed; (4) Dry the nano zirconium oxide powder treated in step (3) for more than 6 hours, grind it mechanically, and pass it through an 80-mesh sieve for standby use.

[0033] Example 4: Pretreatment of Nano-zirconia Powders The difference between this example and example 1 is that the surface modifier is replaced by silane coupling agent KH560, which can also be replaced by KH550 or KH570.

[0034] Example 5: Pretreatment of Nano-zirconia Powder The difference between this embodiment and embodiment 1 is that the surface modifier is replaced by an aluminate coupling agent, and can also be replaced by a zirconate coupling agent or an aluminum-titanium composite coupling agent JTW-1618.

[0035] Example 6 Preparation of photosensitive resin mixed solution: By weight (1 part in this embodiment is 1 kg), take 0.6 parts of monofunctional monomer (2-hydroxyethyl acrylate (HEA), then add 2.4 parts of multifunctional monomer (1.6-hexanediol diacrylate (HDDA) and stir to mix evenly; then add 1 part of prepolymer (polyurethane acrylate), add 0.5 parts of polyether dispersant (Solsperse 17000 from Lubrizol) as dispersant, and then add 0.5 parts of plasticizer (polybutene), stir to mix evenly, and obtain a resin without photoinitiator component.

[0036] To the resin without photoinitiator component, 0.05 parts of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMBA), 0.01 parts of light absorber salicylate UV absorber (ethylhexyl salicylate), 0.001 parts of light inhibitor (tetraethylthiuram disulfide), 0.001 parts of up-conversion particles: doped with trivalent rare earth ions (Yb 3 +) zirconium oxide, and stirred and mixed evenly to obtain a photosensitive resin mixed liquid for photocurable ceramic slurry, with a viscosity of ≤24.43mPa·s.

[0037] Example 7 Preparation of photosensitive resin mixed solution: By weight (1 part in this embodiment is 1 kg), take 3 parts of monofunctional monomer (a mixture of 2-hydroxypropyl acrylate (HPA) and lauryl acrylate (LA) in a mass ratio of 1:1), and then add 12 parts of multifunctional monomer (a mixture of hydroxyethyl methacrylate (HEMA) + ethoxylated pentaerythritol tetraacrylate (PPTTA) in a mass ratio of 1:1) and stir and mix evenly; then add 6 parts of prepolymer (a mixture of polyester acrylate + epoxy acrylate in a mass ratio of 1:1), add 12 parts of dispersant: a mixture of polyether dispersant (Solsperse 24000 of Lubrizol) + polyacrylate dispersant (Disperse-AVD 15 of Daniel Company, USA) in a mass ratio of 1:1, and then add 12 parts of plasticizer (a mixture of polyethylene glycol 400 + polypropylene glycol in a mass ratio of 1:1), stir and mix evenly to obtain a resin without a photoinitiator component.

[0038] To the resin without photoinitiator component, 0.5 parts of photoinitiator (mixture of UV-184 + TPO in a 1:1 mass ratio), 0.5 parts of light absorber (mixture of UV-327 + UV1557 in a 1:1 mass ratio), 0.1 parts of photoinhibitor (mixture of p-methoxyphenol + 2,4,6-trinitrophenol in a 1:1 mass ratio), 0.1 parts of upconversion particles: doped with trivalent rare earth ions (Er 3A mixture of yttrium oxide doped with trivalent rare earth ions (Ho3+) and zirconium oxide doped with trivalent rare earth ions (Ho3+) in a mass ratio of 1:1 was stirred and mixed uniformly to obtain a photosensitive resin mixed liquid for photocurable ceramic slurry with a viscosity of 27.1 mPa·s.

[0039] Example 8 Preparation of photosensitive resin mixed solution: By weight (1 part in this embodiment is 1 kg), take 2 parts of monofunctional monomer (glycidyl acrylate (GA)), then add 6 parts of multifunctional monomer (dipentaerythritol hexaacrylate (DPHA)) and stir to mix evenly; then add 3 parts of prepolymer (polyester acrylate), add 6 parts of dispersant: Dow Chemical Company HYPODTM 8503, and then add 6 parts of plasticizer (tributyl citrate), stir to mix evenly, and obtain a resin without photoinitiator component.

[0040] To the resin without photoinitiator component, 0.2 parts of photoinitiator (2-hydroxy-2-methyl-p-hydroxyethyl ether phenyl acetone-1), 0.2 parts of light absorber (UV-928), 0.05 parts of light inhibitor (hydroquinone), 0.05 parts of up-conversion particles: doped with trivalent rare earth ions (Tm 3 +) of yttrium oxide, stirred and mixed evenly to obtain a photosensitive resin mixed liquid for photocurable ceramic slurry, with a viscosity of 21.65 mPa·s.

[0041] Example 9-12 Preparation of photosensitive resin mixed solution: The difference from Example 8 is that the monofunctional monomers are replaced by: Example 9: isobornyl acrylate (IBOA), Example 10: tetrahydrofurfuryl acrylate (THFA), Example 11: dioxolyl acrylate, isobornyl acrylate (IBOA), Example 12: cyclotrimethylolpropane formal acrylate (CTFA).

[0042] Example 13-15 Preparation of photosensitive resin mixed solution: The difference from Example 8 is that the multifunctional monomers are replaced by: Example 13: trimethylolpropane triacrylate (TMPTA), Example 14: ethoxylated trimethylolpropane triacrylate (TMP6EOTA), Example 15: polyethylene glycol diacrylate (PEGDA).

[0043] Example 16 Preparation of photosensitive resin mixed solution: The difference from Example 8 is that the plasticizer is replaced by diisononyl cyclohexane 1,2-dicarboxylate.

[0044] Example 17 Preparation of photosensitive resin mixed solution: The difference from Example 8 is that the plasticizer is replaced by epoxidized soybean oil.

[0045] Example 18-38 Preparation of photosensitive resin mixed solution: The difference from Example 8 is that the light absorbers are replaced by: Example 18: trimethylcyclohexyl salicylate, Example 19: octyl salicylate, Example 20: phenyl salicylate, Example 21: isohexadecanyl salicylate, Example 22: hexyl salicylate, Example 23: ethylene glycol salicylate, Example 24: benzyl salicylate, Example 25: benzophenone-4 (UV-9), Example 26: benzophenone-8 (UV-5411), Example 27: benzophenone-5 (BP-5), Example 28: 2,2'-methylenebis(4-tert-octyl-6-benzotriazolephenol (UV360), Example 29: 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole (UV329), Example 30: 2,2-(2 '-Hydroxy-3',5'-bis(a,a-dimethylbenzyl)phenyl)benzotriazole (UV-234), Example 31: 2,4-diphenyl-6-(2-hydroxyphenyl)-1,3,5-triazine (UV1164), Example 32: 2,2'-Hydroxy-5,5'-diphenyl-1,3,5-triazine (UV360), Example 33: 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (UV400), Example 34: 2,4-bis-(2-ethylhexyloxy)-6-(2-hydroxyphenyl)-1,3,5-triazine (UV479), Example 35: Tinuvin 123. Example 36: Tinuvin 144. Example 37: Bis(2,2,6,6-tetramethylpiperidinyl)sebacate (UV770). Example 38: Chimassorb 119.

[0046] Example 39-40 Preparation of photosensitive resin mixed solution: The difference from Example 8 is that the photoinhibitors are replaced by: Example 39: 1,4-benzoquinone, Example 40: 2,6-di-tert-butyl-p-cresol.

[0047] Example 41-42 Preparation of photosensitive resin mixed solution: The difference from Example 8 is that the upconversion particles are replaced by: Example 41: Doping with trivalent rare earth ions (Yb 3 +) lanthanum oxychloride, Example 42: doped with trivalent rare earth ions (Er 3 +) yttrium oxysulfide.

[0048] Preparation of Photosensitive Resin Mixture in Examples 43-47: The difference from Example 8 is that the dispersant is replaced by: Example 43: Solsperse 40000 / 41000 from Lubrizol, Example 44: Polyester dispersant (Hypersol L4742 / L4744 from KVK, Denmark), Example 45: Polyester dispersant (DISPER BYK (Anti-Terra-U, Anti-Terra-U80, 103, 2152, UV3570, 4510) from German BYK Chemicals), Example 46: Polyacrylate dispersant (Disperse-AVD 15 from Daniel Company, USA and Elvacite AB1010 from DuPont Company, Example 47: Polyacrylate type dispersant (DISPER BYK (110, 111, 142, 180, 906, 2000, 2205, 9077) manufactured by German BYK Chemical).

[0049] Example 48: Preparation of Ceramic Oral Prosthesis 1. Preparation of photocurable ceramic slurry: 79 kg of pretreated nano zirconium oxide powder prepared in Example 1 and 21 kg of photosensitive resin mixed solution prepared in Example 6 were added to the mixed photosensitive resin and mixed for 2 hours in a ball mill at 300 rpm / min. After mixing, the slurry was filtered into a plastic container with a 200-mesh filter and vacuum-defoamed for 1 hour at a vacuum degree of 0.1 kPa to finally obtain an ideal ceramic printing slurry. The slurry viscosity was 5.14 Pa·s.

[0050] 2. Preparation of the formed body: The digital files of missing anterior and posterior teeth obtained by scanning the intraoral or plaster models in the hospital or laboratory are input into the digital CAD design software for dental restorations. The designer accurately designs the digital files of dental restorations such as anterior and posterior single crowns. The design files include the shape of the restoration, marginal tightness, occlusion and adjacent relationships, and the shape required for the early healing of the gums.

[0051] The designed restoration file was scaled in the proprietary software (Materialise Magics). According to the scale ratio determined in the previous step, it was enlarged by 1.3 times in the three directions of X, Y, and Z. At the same time, the proprietary software (Materialise Magics) was used to add support structures and substrates to the scaled restoration. Finally, the restoration file was converted into a slice format file with a specified layer thickness (25um layer thickness) through the slice software (Materialise Magics).

[0052] The stable ceramic printing slurry is placed in the material tank of a sunken 405nm DLP printer for photocuring printing. Each layer is printed with a thickness of 25um and the printing exposure is 6s. The UV curing process is repeated until a complete printed green body is printed. Then, the residual printing slurry on the surface is cleaned for 5min using a 50Hz ultrasonic cleaner, and the cleaning is repeated 3 times. After cleaning, the printed green body is dried using a microwave dryer. Finally, the support structure on the printed part is removed using a grinding and polishing tool, and a printed part with a good surface condition is obtained; 3. Debinding: The molded body is debinded in the air by heat preservation in sections; First glue removal point: heat up to 120℃ at a rate of 2℃ / min and keep warm for 5h; Second glue discharge section point: heat up to 240℃ at a rate of 2℃ / min and keep warm for 5h; The third glue discharge section point: heat up to 340℃ at a rate of 2℃ / min and keep warm for 5h; Fourth glue discharge point: heat up to 500℃ at a rate of 0.2℃ / min, keep warm for 5h 4. Sintering: Three-stage sintering The first sintering stage: heating to 300°C at a rate of 2°C / min and keeping at this temperature for 2h; The second sintering stage: the temperature is raised to 1100℃ at a rate of 10℃ / min and kept at this temperature for 2h; at this time, the relative density of the green body is about 71%; the third sintering stage: the temperature is raised to 1650℃ at a rate of 50℃ / min and kept at this temperature for 2h; after completing this stage, a ceramic restoration with a relative density of more than 99% is obtained, and the scanning fitting method is used for testing, and the accuracy error is 78um; 5. Grinding and polishing: Grind and polish the sintered restoration.

[0053] Example 49: Preparation of Ceramic Oral Prosthesis The difference from Example 48 is that 85 kg of pretreated nano-zirconia powder and 15 kg of photosensitive resin mixed liquid are used to obtain a photocurable ceramic slurry with a viscosity of 9.05 Pa·s.

[0054] Example 50: Preparation of Ceramic Oral Prosthesis The difference from Example 48 is that 83 kg of pretreated nano-zirconia powder and 17 kg of photosensitive resin mixed liquid are used to obtain a photocurable ceramic slurry with a viscosity of 11.88 Pa·s.

[0055] Example 51: Preparation of Ceramic Oral Restoration The difference from Example 48 is that the debinding atmosphere is adjusted to argon, and a final oral restoration with a relative density of more than 99% is obtained.

[0056] Example 52: Preparation of Ceramic Oral Restoration The difference from Example 48 is that the debinding atmosphere is adjusted to nitrogen, and a final oral restoration with a relative density of more than 99% is obtained.

[0057] Example 53: The preparation of a ceramic oral restoration is different from that of Example 48 in that the debinding atmosphere is adjusted to a vacuum, and a final oral restoration with a relative density of more than 99% is obtained.

[0058] Example 54: The preparation of a ceramic oral restoration is different from that of Example 48 in that the single crown restoration prepared from the molded body is replaced by an inlay, and the scanning fitting method is used for testing, with an accuracy error of 88um.

[0059] Example 55: Preparation of Ceramic Oral Restoration The difference from Example 48 is that the single crown restoration prepared from the molded blank is replaced by a bridge The debinding parameters are replaced by First glue removal point: heat up to 100℃ at a rate of 0.05℃ / min and keep warm for 10h; Second glue discharge segmentation point: heat up to 180℃ at a rate of 0.05℃ / min and keep warm for 10h; The third glue discharge section point: heat up to 300℃ at a rate of 0.05℃ / min and keep warm for 10h; Fourth glue discharge point: heat up to 400℃ at a rate of 0.05℃ / min and keep warm for 10h; The sintering parameters are replaced by The first sintering stage: heating to 200°C at a rate of 1°C / min and keeping at this temperature for 10h; The second sintering stage: heating to 1100°C at a rate of 5°C / min and keeping at this temperature for 10h; The third sintering stage: heating to 1400℃ at a rate of 5℃ / min and keeping at this temperature for 10h; The final relative density of the oral restoration was more than 99%, and the scanning fitting method was used for testing, with an accuracy error of 108um.

[0060] Example 56: Preparation of Ceramic Oral Prosthesis The difference from Example 48 is that the single crown restoration prepared from the molded blank is replaced with a veneer. The debinding parameters are replaced by First debonding point: heat up to 150℃ at a rate of 10℃ / min and keep warm for 0.5h; Second glue discharge section point: heat up to 280℃ at a rate of 10℃ / min and keep warm for 0.5h; The third glue discharge section point: heat up to 380℃ at a rate of 10℃ / min and keep warm for 0.5h; Fourth glue discharge point: heat up to 600℃ at a rate of 10℃ / min and keep warm for 0.5h; The sintering parameters are replaced by The first sintering stage: heating to 200°C at a rate of 50°C / min and keeping at this temperature for 1h; The second sintering stage: heating to 1200℃ at a rate of 50℃ / min and keeping at this temperature for 1h; The third sintering stage: heating to 1700℃ at a rate of 200℃ / min and keeping at this temperature for 1h; The final relative density of the oral restoration was more than 99%, and the scanning fitting method was used for testing, with an accuracy error of 58um.

[0061] Example 57: Preparation of Ceramic Oral Prosthesis The difference from Example 48 is that: The sintering parameters are replaced by The first sintering stage: heating to 400°C at a rate of 100°C / min and keeping at this temperature for 0.5h; The second sintering stage: heating to 1400℃ at a rate of 200℃ / min and keeping at this temperature for 0.5h; The third sintering stage: heat up to 1700°C at a rate of 200°C / min and keep warm for 0.5h.

[0062] Example 58: Preparation of Ceramic Oral Prosthesis The single crown restoration prepared from the molded blank in Example 48 was replaced with a 4mm*3mm*25mm strip, and 10 strips were prepared and printed in the 0° direction. The debinding parameters are replaced by: First glue removal point: heat up to 100℃ at a rate of 10℃ / min and keep warm for 0.5h; Second glue discharge section point: heat up to 180℃ at a rate of 10℃ / min and keep warm for 0.5h; The third glue discharge section point: heat up to 380℃ at a rate of 10℃ / min and keep warm for 0.5h; Fourth glue discharge point: heat up to 600℃ at a rate of 1℃ / min and keep warm for 0.5h; The sintering parameters are replaced by The first sintering stage: heating to 200°C at a rate of 50°C / min and keeping at this temperature for 1h; The second sintering stage: heating to 1200℃ at a rate of 50℃ / min and keeping at this temperature for 1h; The third sintering stage: heating to 1700℃ at a rate of 200℃ / min and keeping at this temperature for 1h; The final relative density of the sample is above 99%. At the same time, the three-point bending strength test is carried out according to GB30367, and the final result is 1052MPa.

[0063] Example 59: Preparation of Ceramic Dental Restoration The difference from Example 58 is that the printing is performed in a 90° direction. The final relative density of the sample is above 99%. At the same time, the three-point bending strength test is carried out according to GB30367, and the final result is 860MPa.

[0064] All examples were used to prepare 4 mm*3 mm*25 mm standard strength test strips for strength testing.

[0065] Comparative Example 1: The monofunctional monomer (a mixture of 2-hydroxypropyl acrylate (HPA) and lauryl acrylate (LA) in a mass ratio of 1:1) and the multifunctional monomer (a mixture of hydroxyethyl methacrylate (HEMA) + ethoxylated pentaerythritol tetraacrylate (PPTTA) in a mass ratio of 1:1) in Example 7; and the prepolymer (a mixture of polyester acrylate + epoxy acrylate in a mass ratio of 1:1) are replaced with the resin in CN106007671B, and other process conditions remain unchanged. The influence of sintering density is investigated: the density of Example 7 is 6.00 g / cm3, the three-point flexural strength is 1032 MPa, and the average light transmittance of 1 mm thickness is 12%. The density of the comparative example is 5.8 g / cm3, the three-point flexural strength is 652 MPa, and the average light transmittance of 1 mm thickness is 6%; the lower the density, the less light transmittance and the poorer the aesthetic performance. The density of ceramics after sintering in the prior art process can only reach 5.9 g / cm3 at most. The present invention significantly improves the density of ceramics after sintering, thereby greatly improving the strength and transparency.

[0066] Comparative Example 2: In Example 55, no plasticizer was added, and other process conditions remained unchanged. Whether cracking occurred during the debinding sintering of the 3-unit bridge body was investigated. Figure 1As shown, the three-unit bridge bodies processed in Example 55 did not crack, while the three-unit bridge bodies processed in Comparative Example 2 cracked significantly, which indicates that the combination of plasticizer and photosensitive resin can simultaneously inhibit the occurrence of debinding sintering cracking.

[0067] Comparative Example 3: The high-functionality monomer in Example 56 was replaced with a crosslinker monomer (ethoxylated bisphenol A acrylate) having a rigid structure in CN108249930B, and other process conditions remained unchanged to explore its effect on the preparation of 0.1 mm restorations: Figure 3 As shown, the present invention can prepare a complete ultra-thin restoration with a thickness of 0.1 mm, while the comparative example 3 has obvious fracture and delamination, and the strength is insufficient ( Figure 4 ), it can be seen that Comparative Example 3 cannot produce an ultra-thin restoration with a thickness of 0.1 mm.

[0068] Comparative Example 4: Prepare a 4mm*3mm*25mm standard strength test strip using the method of Example 1 in CN106810215B; Compared with the 4mm*3mm*25mm standard strength test strip prepared by the process of Example 59; The influence of the difference in strength in the printing direction was investigated: the 90° printing bending strength of the printed part was reduced from 860 MPa (Example 59) to 278 MPa (Comparative Example 4). Figure 5-6 As shown, comparative example 4 has obvious delamination after sintering.

[0069] Comparative Example 5: The method of Example 58 was used, and the sintering process was changed to 5°C / min and the temperature was raised to 1700°C to prepare a 4mm*3mm*25mm standard strength test strip; Compared with the 4mm*3mm*25mm standard strength test strip prepared by the process of Example 58; The influence of the difference in strength in the printing direction was investigated: the bending strength of the printed part decreased from 1052 MPa (Example 58) to 678 MPa (Comparative Example 5), and there were more pores after interlayer sintering ( Figure 7 ).

[0070] Comparative Example 6: In Example 55, the binder removal process was changed to 0.1°C / min heating to 400°C, and the temperature was kept for 10 hours. Other process conditions remained unchanged to investigate whether cracking occurred during the binder removal sintering of the three-unit bridge. The three-unit bridge processed in Example 55 did not crack, while the three-unit bridge processed in Comparative Example 6 had obvious cracking (compared to Figure 2 This shows that a reasonable debinding system can prevent the occurrence of cracking.

[0071] The above-described embodiment is only a preferred solution of the present invention and does not limit the present invention in any form. There are other variations and modifications without exceeding the technical solution described in the claims.

Claims

1. A zirconia ceramic material suitable for photocuring additive manufacturing, characterized in that: The raw material is composed of nano zirconium oxide powder and photosensitive resin mixed liquid, wherein the content of nano zirconium oxide powder is more than 79wt%; The particle size of the nano zirconium oxide powder is 10-400 nanometers; In parts by weight, the photosensitive resin mixture is prepared by mixing 0.6 to 3 parts of a monofunctional monomer, 2.4 to 12 parts of a multifunctional monomer, 1 to 6 parts of a prepolymer, 0.5 to 12 parts of a dispersant, 0.5 to 12 parts of a plasticizer, 0.05 to 0.5 parts of a photoinitiator, 0.01 to 0.5 parts of a light absorber, 0.001 to 0.1 parts of a light inhibitor, and 0.001 to 0.1 parts of upconversion particles.

2. The zirconia ceramic material according to claim 1, characterized in that: The nano zirconium oxide powder is used after being pretreated, and the pretreatment method is as follows: (1) Dry the nano zirconium oxide powder to a moisture content of ≤1%; (2) 100 parts of anhydrous ethanol and 0.1-6 parts of a surface modifier are mixed by weight, and then 30-80 parts of dried nano zirconium oxide powder are added, stirred at 50-80° C. for 2-6 hours, centrifuged, the supernatant is discarded, and dried; (3) adding the dried nano zirconium oxide powder to 100 parts by weight of anhydrous ethanol, ultrasonically dispersing, centrifuging, discarding the supernatant, and drying; Repeat this step 2-3 times; (4) Dry the nano zirconium oxide powder processed in step (3) for more than 6 hours, grind it mechanically, sieve it and set it aside.

3. The zirconia ceramic material according to claim 2, characterized in that: The surface modifier is selected from one or more of stearic acid, oleic acid, titanate coupling agent, silane coupling agent, aluminate coupling agent, zirconate coupling agent, aluminum-titanium composite coupling agent, sulfonated castor oil, and monolipid phosphate.

4. The zirconia ceramic material according to claim 1 or 2, characterized in that: The monofunctional monomer is selected from one or more of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, lauryl acrylate, glycidyl acrylate, isobornyl acrylate, tetrahydrofurfuryl acrylate, dioxolyl acrylate, isobornyl acrylate, and cyclotrimethylolpropane formal acrylate.

5. The zirconia ceramic material according to claim 1 or 2, characterized in that: The multifunctional monomer is one or more selected from 1,6-hexanediol diacrylate, hydroxyethyl methacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, and polyethylene glycol diacrylate.

6. The zirconia ceramic material according to claim 1 or 2, characterized in that: The prepolymer is selected from one or more of polyurethane acrylate, polyester acrylate and epoxy acrylate.

7. The zirconia ceramic material according to claim 1 or 2, characterized in that: The dispersant is selected from one or more of a polyether dispersant, a polyester dispersant, a polyacrylate dispersant, and a polyolefin dispersant; The plasticizer is selected from one or more of polyaliphatic hydrocarbons, polyethylene glycol, polypropylene glycol, tributyl citrate, diisononyl cyclohexane 1,2-dicarboxylate, and epoxidized soybean oil.

8. The zirconia ceramic material according to claim 1 or 2, characterized in that: The photoinitiator is selected from any one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxy-cyclohexyl benzophenone, 2-hydroxy-2-methyl-p-hydroxyethyl ether phenyl acetone-1, and 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide; The light absorber is selected from ethylhexyl salicylate, trimethylcyclohexyl salicylate, octyl salicylate, phenyl salicylate, isohexadecanyl salicylate, hexyl salicylate, ethylene glycol salicylate, benzyl salicylate, benzophenone-3, benzophenone-4, benzophenone-8, benzophenone-5, 2,2'-methylenebis(4-tert-octyl-6-benzotriazolephenol), 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2'- Hydroxy-3',5'-bis(a,a-dimethylbenzyl)phenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)-5-chlorophenyl-2H-triazine, 2,4-diphenyl-6-(2-hydroxyphenyl)-1,3,5-triazine, 2,2'-hydroxy-5,5'-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis-(2-ethylhexyloxy)-6-(2-hydroxyphenyl)-1,3,5-triazine, Tinuvin 123, Tinuvin 144, bis(2,2,6,6-tetramethylpiperidinyl)sebacate, Chimassorb 119 or more thereof; The photoinhibitor is selected from one or more of tetraethylthiuram disulfide, naphthoyl methylene quinuclidine tetraphenyl borate, p-methoxyphenol, 2,4,6-trinitrophenol, 1,4-benzoquinone, hydroquinone, and 2,6-di-tert-butyl-p-cresol; the up-conversion particle is selected from one or more of zirconium oxide doped with trivalent rare earth ions, yttrium oxide doped with trivalent rare earth ions, lanthanum oxychloride doped with trivalent rare earth ions, and yttrium oxysulfide doped with trivalent rare earth ions, and the trivalent rare earth ion is Yb 3 +, Er 3 +, Ho3+ and Tm 3 + one of them.

9. The method for manufacturing a ceramic oral restoration using a zirconia ceramic material according to claim 1, characterized in that: The steps include:

1. Preparation of light-curing ceramic slurry: Mix the nano zirconium oxide powder and the photosensitive resin mixture evenly, sieve, and vacuum degas to obtain the light-curing ceramic slurry; 2. Preparation of the molding body: Using the light-cured ceramic slurry as the raw material, light-cured molding is performed layer by layer on a 3D light-curing molding machine according to the designed restoration shape to obtain the molding body, which is then cleaned with ultrasonic cleaning; 3. Debinding: The molded body is debinded by heat preservation in sections in air, argon, nitrogen or vacuum environment; 4. Sintering: Three-stage sintering The first sintering stage: heating to 200-400℃ at a rate of 1-100℃ / min, keeping temperature for 0.5-10h; The second sintering stage: heating to 1100-1400℃ at a rate of 5-200℃ / min, keeping temperature for 0.5-10h; The third sintering stage: heating to 1400-1700℃ at a rate of 5-200℃ / min, keeping warm for 0.5-10h 5. Grinding and polishing: Grind and polish the sintered restoration.

10. The method according to claim 9, characterized in that The segmented insulation parameters are controlled as follows: First debonding point: heat up to 100-150℃ at a rate of 0.05-10℃ / min, and keep warm for 0.5-10h; Second glue discharge section point: heat up to 180-280℃ at a rate of 0.05-10℃ / min, and keep warm for 0.5-10h; The third glue discharge section point: heat up to 300-380℃ at a rate of 0.05-10℃ / min, and keep warm for 0.5-10h; Fourth row of glue segmentation point: heat up to 400-600℃ at a rate of 0.05-10℃ / min and keep warm for 0.5-10h.

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