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CN-118145989-B - Zirconia ceramic slurry, preparation method and application thereof, 3D printing zirconia ceramic and application thereof

CN118145989BCN 118145989 BCN118145989 BCN 118145989BCN-118145989-B

Abstract

The invention provides zirconia ceramic slurry, a preparation method and application thereof, 3D printing zirconia ceramic and application thereof, and relates to the technical field of material addition. The zirconia ceramic slurry provided by the invention comprises modified zirconia powder, resin premix, an additive, a photoinitiator and a thermal initiator, wherein the modified zirconia powder is obtained by modifying yttria-doped zirconia powder by one or more modifiers selected from methacrylic acid, 3- (methacryloyloxy) propyl trimethoxysilane and stearic acid, and the resin premix comprises acrylic acid ester oligomers and a reactive diluent. The zirconia ceramic slurry provided by the invention has high solid content and low viscosity, is suitable for DLP printers of various types of ultraviolet light and visible light, and the 3D printing zirconia ceramic obtained through 3D printing, photo-curing, thermosetting, degreasing and sintering has high density and excellent mechanical property, and can meet the mechanical property standard of dental restorations.

Inventors

  • WU PING
  • ZHOU SHENGGANG
  • ZHANG JIAXIN
  • WU HAIYAN
  • YANG ZHIKAI

Assignees

  • 爱迪特（秦皇岛）科技股份有限公司

Dates

Publication Date
20260508
Application Date
20240311

Claims (10)

  1. 1. The zirconia ceramic slurry is characterized by comprising, by mass, 75-85% of modified zirconia powder, 5-10% of resin premix, 4-8% of additives, 2-6% of photoinitiators and 0.1-1% of thermal initiators; The modified zirconia powder is obtained by modifying yttria-doped zirconia powder by a modifier, wherein the medium particle size of the yttria-doped zirconia powder is 100-500 nm, the specific surface area is 7-9.5 m 2 /g, the content of yttria is 5-10wt%, the modifier comprises one or more of methacrylic acid, 3- (methacryloyloxy) propyl trimethoxysilane and stearic acid, and the mass of the modifier is 0.4-1% of the mass of the yttria-doped zirconia powder; the resin premix comprises, by mass, 15-40% of acrylic acid ester oligomers and 60-85% of reactive diluents, wherein the acrylic acid ester oligomers are one or more of epoxy acrylic acid ester, polyester acrylic acid ester and polyurethane acrylic acid ester; the reactive diluent is one or more of hydroxyethyl methacrylate, isooctyl acrylate, 1, 6-hexanediol diacrylate, triethylene glycol diacrylate, pentaerythritol triacrylate, tetrahydrofuran methyl acrylate, ditrimethylolpropane tetraacrylate and polyethylene glycol diacrylate.
  2. 2. The zirconia ceramic slurry of claim 1, wherein the photoinitiator comprises one or more of 1-hydroxycyclohexylphenyl ketone, bis 2, 6-difluoro-3-pyrrolophenyl titanocene, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone, diphenyl- (2, 4, 6-trimethylbenzoyl) phosphorus oxide, photoinitiator 1300, and camphorquinone.
  3. 3. The zirconia ceramic slurry of claim 1 wherein the thermal initiator comprises an organic peroxy-based initiator, the organic peroxy-based initiator being at least one of dicumyl peroxide, dibenzoyl peroxide, t-butyl hydroperoxide.
  4. 4. The zirconia ceramic slurry of claim 1 wherein the additive comprises one or more of a surfactant, a dispersant, or a defoamer.
  5. 5. The zirconia ceramic slurry according to claim 4, wherein the surfactant comprises one or more of a silane coupling agent, polyvinylpyrrolidone, a lower alcohol, an organic amine, a carboxylic acid, a carboxylate, a sulfate, and a sulfonate.
  6. 6. The zirconia ceramic slurry of claim 4 wherein the dispersant comprises one or more of stearic acid, oleic acid, polyvinylpyrrolidone, sodium polyacrylate, polypropoxy Ji Sanyuan ammonium chloride, ammonium polyacrylate, silane coupling agent, BYK103, KOS110, KOS163, solsperse 2000, di-high 685, yet high 9030 and yet high 9070.
  7. 7. The method for preparing the zirconia ceramic slurry according to any one of claims 1 to 6, comprising the steps of: Mixing the modified zirconia powder, the resin premix and the additive to obtain zirconia-resin slurry; and mixing the zirconia-resin slurry, the photoinitiator and the thermal initiator to obtain zirconia ceramic slurry.
  8. 8. The 3D printing zirconia ceramic is characterized in that 3D printing, photo-curing, thermosetting, degreasing and sintering are sequentially carried out on zirconia ceramic slurry to obtain the 3D printing zirconia ceramic; The zirconia ceramic slurry is the zirconia ceramic slurry according to any one of claims 1 to 6 or the zirconia ceramic slurry prepared by the preparation method according to claim 7.
  9. 9. The 3D printed zirconia ceramic of claim 8 wherein the photo-cured green body has a density of 3.1g/cm 3 or more; the density of the double-cured biscuit obtained by heat curing is 3.13-3.9 g/cm 3 .
  10. 10. Use of the zirconia ceramic slurry of any one of claims 1 to 6, the zirconia ceramic slurry produced by the production method of claim 7 or the 3D printed zirconia ceramic of any one of claims 8 to 9 for the production of dental restorations.

Description

Zirconia ceramic slurry, preparation method and application thereof, 3D printing zirconia ceramic and application thereof Technical Field The invention relates to the technical field of material increase, in particular to zirconia ceramic slurry, a preparation method and application thereof, 3D printing zirconia ceramic and application thereof. Background The zirconia ceramics have the structural properties of high strength, high hardness, high temperature resistance, corrosion resistance, high gloss and the like, have rich functionalities of dielectric, piezoelectric, semiconductor, acousto-optic, superconducting, magnetic, biocompatibility and the like, and are widely applied to various national defense and civil fields such as aerospace, 5G communication, sensors, biomedicine, jewelry and the like. The photocuring 3D printing technology is a new technical approach for preparing, processing and producing dental ceramic materials, and has the advantages of digitalization, intelligence, high precision, high efficiency, personalized customization, batch production, easiness in molding products with complex shapes and the like. The medical image model of the teeth is obtained only through oral cavity scanning, CT or CBCT scanning, then three-dimensional reconstruction is carried out, and the personalized all-ceramic dental crown restoration such as dental crowns, inlays, onlays, veneers, dental bridges and the like can be rapidly manufactured through a 3D printing technology. At present, the bending strength of the full porcelain tooth prepared by the traditional process can reach more than 1200 MPa. The density of the 3D printing full-ceramic dental crown is about 95%, and the bending strength is mostly 500-600 MPa, even less than half of the full-ceramic dental crown prepared by the traditional process. The key problems of restricting the industrialization of the 3D printing all-ceramic dental crown restoration are lower density and poorer mechanical property of the material after printing and sintering. Disclosure of Invention In view of the above, the invention aims to provide a zirconia ceramic slurry, a preparation method and application thereof, a 3D printing zirconia ceramic and application thereof. The zirconia ceramic slurry provided by the invention has high solid content, low viscosity and high double bond conversion efficiency after photo-setting and thermal setting, and can obviously improve the density and mechanical properties of the 3D printing zirconia ceramic. In order to achieve the above object, the present invention provides the following technical solutions: the invention provides zirconia ceramic slurry, which comprises, by mass, 75-85% of modified zirconia powder, 5-10% of resin premix, 4-8% of additives, 2-6% of photoinitiators and 0.1-1% of thermal initiators; The modified zirconia powder is obtained by modifying yttria-doped zirconia powder by a modifier, wherein the medium grain size of the yttria-doped zirconia powder is 100-500 nm, the specific surface area of the yttria-doped zirconia powder is 7-9.5 m 2/g, the content of yttria is 5-10wt%, and the mass of the modifier is 0.4-1% of the mass of the yttria-doped zirconia powder. Preferably, the modifier comprises one or more of methacrylic acid, 3- (methacryloyloxy) propyl trimethoxysilane and stearic acid. Preferably, the resin premix comprises, by mass, 15-40% of acrylic oligomers and 60-85% of reactive diluents. Preferably, the reactive diluent comprises one or more of hydroxyethyl methacrylate, isooctyl acrylate, 1, 6-hexanediol diacrylate, triethylene glycol diacrylate, pentaerythritol triacrylate, tetrahydrofuran methyl acrylate, ditrimethylolpropane tetraacrylate and polyethylene glycol diacrylate. Preferably, the photoinitiator comprises one or more of 1-hydroxycyclohexyl phenyl ketone, bis 2, 6-difluoro-3-pyrrolyl titanocene, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone, diphenyl- (2, 4, 6-trimethylbenzoyl) phosphorus oxide, photoinitiator 1300 and camphorquinone. Preferably, the thermal initiator comprises at least one of an organic peroxy-based initiator such as dicumyl peroxide, dibenzoyl peroxide, t-butyl hydroperoxide. Preferably, the additive comprises one or more of a surfactant, a dispersant or a defoamer. Preferably, the surfactant comprises one or more of silane coupling agent, polyvinylpyrrolidone, lower alcohol, organic amine, carboxylic acid, carboxylate, sulfate and sulfonate. Preferably, the dispersing agent comprises one or more of stearic acid, oleic acid, polyvinylpyrrolidone, sodium polyacrylate, polypropoxy Ji Sanyuan ammonium chloride, polyacrylate ammonium, a silane coupling agent, BYK103, KOS110, KOS163, solsperse 2000, digao 685, shanggao 9030 and Shanggao 9070. The invention provides a preparation method of zirconia ceramic slurry, which comprises the following steps: Mixing the modified zirconia powder, the resin premix and the additive to obtain